1

SURFACE CHEMISTRY

 Surface chemistry is the branch of physical chemistry which deals with the phenomenon that occur at
the surfaces.

 The physical boundary of any condensed phase is called a surface.

NOTE:-

 The term surface is used generally when a solid surface is in contact with gases.

 A more general term ‘interface’ is common in place of surface. An interface separates two
immiscible materials.

 Due to complete miscibility there is no interface between the gases.

 Adsorption and catalysis are important surface phenomenon.

ADSORPTION

 It is the phenomenon of attracting and retaining the molecules of a substance at the surface of a solid
or liquid rather than in bulk.

 It is responsible for higher concentration of any molecular species at the surface than in the bulk.

 It is a spontaneous process and during adsorption there is decrease in free energy.

 It is exothermic process.

ADSORBENT:-

 It is the substance whose surface has been utilized for adsorption.

ADSORBATE:-

 It is the substance whose molecules accumulate on the surface of adsorbent.

 The adsorbent may be solid or liquid and the adsorbate may be gas or a solute in some solution.

 The adsorption of gases on metal surfaces is called occlusion.

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Ads orba te
( ga s or s olute )

Ads orbe nt
( s ol i d)

Example:

 Activated charcoal which is finely divided has a tendency to adsorb a number of gases like ammonia,
phosgene etc. Here charcoal acts as an adsorbent while gas molecules act as adsorbate.

 In a similar manner, animal charcoal is used for decolourising a number of organic substances in the
form of their solution. The discharge of the colour is due to fact that the coloured component
(generally an organic dye) gets adsorbed on the surface of the adsorbent i.e. animal charcoal.

EXPLANATION OF ADSORPTION:

 The adsorption is a surface phenomenon. The atoms in a solid are held together by certain binding
forces which are mainly van der Waals’ forces or may be even chemical forces.

 The unutilized or unbalanced forces present on the surface (indicated by dotted lines) make it quite
active. Moreover, when a solid substance shown in figure 1 (a) is broken into two or more pieces,
new surfaces get formed shown in figure 1 (b) i.e., the number of the unbalanced forces becomes
more.

 In other words, the number of active centres or free valencies becomes more by taking the adsorbent
in the finely powdered form.

X X X X

X X X X

(a) (b)
Figure 1: Unbalanced forces on the finely divided solid surface

 Due to the unbalanced forces, the atoms or molecules on the surface have a tendency to attract and
retain the molecules of the gases or liquids when they come in contact with the surface.

 This results into higher concentration of any particular species at the surface than in the bulk and
this leads to adsorption.

 The absorbent which are commonly used are activated charcoal, animal charcoal, silica gel and a
number of finely divided metals such as Cu, Ni, Pd, etc.
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 Activated charcoal is a powerful adsorbent since it is a microscopic crystalline variety of

graphite having a very large surface area.

THERMODYNAMICAL FEASIBILITY OF ADSORPTION:

 The phenomenon adsorption arises because of attraction between the particles or molecules of
adsorbent and adsorbate. Therefore, it is exothermic in nature and is accompanied by release in energy
known as enthalpy of adsorption (heat of adsorption).
In other words,  H of adsorption is always negative.

 When a gas is adsorbed, the freedoms of movement of its molecules become restricted. This
amounts to decrease in the entropy of the gas after adsorption, i.e.,  S is negative. Adsorption is
thus accompanied by decrease in enthalpy as well as decrease in entropy of the system.

 For a process to be spontaneous, the thermodynamic requirement is that, at constant temperature and
pressure,  G must be negative, i.e., there is a decrease in Gibbs energy.

 On the basis of equation, ΔG = ΔH- TΔS , Δ G can be negative if Δ H has sufficiently high
negative value as – T Δ S is positive. Thus, in an adsorption process, which is spontaneous, a
combination of these two factors makes Δ G negative.

 As the adsorption proceeds, Δ H becomes less and less negative ultimately Δ H becomes equal to T
Δ S and Δ G becomes zero. At this state equilibrium is attained.

DIFFERENCES BETWEEN ADSORPTION AND ABSORPTION

ADSORPTION ABSORPTION
It is a surface phenomenon i.e. it occurs only at It is a bulk phenomenon, i.e., it occurs through
the surface at the adsorbent out the body of the material
In this phenomenon the concentration on the In this phenomenon the concentration is same
surface of adsorbent is different from that in the throughout the material.
bulk
Adsorption is rapid in the beginning and its rate Its rate remains same throughout the process.
slowly decreases with the non-availability of the
surface
It is exothermic process. No significant change occurs.

water vapour

anhydrous CaCl2

silica gel

adsorption absorption
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POSITIVE ADSORPTION:-

 When the concentration of the adsorbate is more on the surface of adsorbent relative to its
concentration in the bulk, it is called positive adsorption.

NEGATIVE ADSORPTION:-

 When the concentration of the adsorbate is less on the surface relative to its concentration in the
bulk, it is called negative adsorption.

SORPTION:-

 The term sorption is used to describe when adsorption and absorption both occurs simultaneously.

X X X
X X X XX X
XX X X
X X X
X X X X X X X X X
X X X
X X
X X X X X X X
X
X
X X X X X
X X X X X X X X X
X X
X X X X X X X
X X X X X X X X
X X X X X
X X X X X X
X
X X X X X X X X X X
X X X X X X X X
X X X
X X
X X X X
X X X X X
X X

ADS OR P TION AB S OR P TION S OR P TION

TYPES OF ADSORPTION:-

 On the basis of binding forces acting between the adsorbate and adsorbent molecules adsorption may
be of two types. They are

(1) Physical adsorption or physisorption or Vander Waal’s adsorption

(2) Chemical adsorption or chemisorptions or activated adsorption.

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DIFFERENCES BETWEEN PHYSISORPTION AND CHEMISORPTION

S.No. Property Physisorption Chemisorption

1 Nature of adsorption Adsorption is weak Adsorption is strong
Easy since weak van der Waals Not easy since chemical forces
2 Ease of desorption
forces are involved are involved
3 Reversibility of process Reversible and occurs rapidly Irreversible and occurs slowly
4 Energy of activation Insignificant and very low Significant and relatively high
Not specific since it takes place Highly specific since it takes place
5 Specificity of adsorption
on the surface of any solid on specified surfaces only
Effect of temperature on Extent of adsorption decreases Extent of adsorption increases
6
adsorption with increase in temperature with increase in temperature
Increases with increase in
Effect of pressure on Pressure of adsorbate gas has a
7 pressure of adsorbate gas and
adsorption negligible effect
finally attains a limiting value
Number of absorbate
8 Usually multilayered Only unilayered
layers formed
Dependence on the
Depends on the nature of adsor- Depends on nature of adsorbate as
nature
9 bate gas only. Easily liquefiable well as adsorbent. No corelation
of the adsorbate and the
gases are readily absorbed can be given
adsorbent
Increases with increases in Increases with increases in surface
10 Surface area of adsorbent
surface area of adsorbent area of adsorbent

H H H H H H

Ni Ni Physisorption Ni Ni Chemisorption Ni Ni
 
Ni Ni Ni Ni Ni Ni

CHEMISORPTION OF HYDROGEN ON NICKEL

NOTE:-

 All the gases show physisorption on solid surfaces eg:- H2/Pd, N2 / charcoal etc

 When a gas may show physisorption as well as chemisorptions at a surface there may be
transition from physisorption to chemisorption as the temperature is raised.

 Adsorption of O2 on tungsten surface is an example of chemisorptions. The film formed at the

surface is not of normal oxide and has different chemical properties.
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 When more than one type of adsorbate species are in contact with a particular adsorbent then
there is a competition between their particles or molecules to be adsorbed on the solid surface.
This depends upon their nature. However the one which can form stronger bonds is adsorbed
more in preference to the other. This is known as competing adsorption and it also happens in
the reverse process i.e., desorption. In this case the species which is weakly adsorbed is
dislodged first from the solid surface.

FACTORS INFLUENCING ADSORPTION OF GASES ON SOLID SURFACES:-

 The extent of adsorption of a gas on a solid surface is affected by the following factors:

(1) Nature of adsorbate gas

(2) Nature and specific area of adsorbent
(3) Effect of pressure
(4) Effect of temperature

NATURE OF ADSORBATE GAS:-

 Easily liquefiable, coloured and smelling gases like NO2, NH3 etc are easily adsorbed on porous
materials like silica gel, charcoal etc. This forms an example of physisorption.
 Permanent gases like H2, N2 and O2 are adsorbed on metals and show chemisorptions.
 Higher the critical temperature of a gas greater is the amount of that gas adsorbed.
 Critical temperatures and rate of adsorption of gases is in the following order

H2O (647.3 K) > SO2 (430 K) > NH3 (405.5K) > HCl (324 K) > CO2 (304.2 K) > CH4 ((190.7K) >
O2 (154.4K)> Ar (151 K) > N2 (126 K) > H2 (33.5 K) > He (5.3 K)

NATURE AND SPECIFIC AREA OF ADSORBENT:-

 Porous materials like silica gel, charcoal etc undertake physisorption because of larger surface
area.
 Transition metals undertake chemisorption due to vacant or half filled d – orbitals.

EFFECT OF PRESSURE:-
 The extent of adsorption of gas per unit mass of adsorbent depends upon the pressure of the gas.
 The variation in the amount of gas adsorbed by the adsorbent with pressure at constant temperature
can be expressed by the means of adsorption isotherm.
 The extent of adsorption is usually expressed as x/m where x is the mass of adsorbate and m is the
mass of adsorbent.
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x/m T constant

O P Ps
 The extent of adsorption (x/m) increases with pressure and reaches maximum corresponding to
pressure Ps called equilibrium pressure.
 Since adsorption is a reversible process desorption also takes place simultaneously.
 At this pressure (Ps) the amount of gas adsorbed becomes equal to the amount of gas desorbed so
that the extent of adsorption becomes constant even though the pressure is increased. This state is
also called saturation state and Ps is called saturation pressure.

FREUNDLICH ADSORPTION ISOTHERM:-

 The mathematical relations of extent of adsorption (x/m) with pressure at constant temperature and
corresponding graphs are studied by Freundlich, are called Freundlich adsorption isotherm.

i) From the adsorption isotherm, it is clear that at low pressure, the graph is almost straight. This
means that x/m is directly proportional to the pressure. It follows first order kinetics. This may
be expressed as

x x
α p1 = K p1
m m
Where K is constant.
ii) At high pressure: The value of x/m becomes almost constant, i.e., it does not change with the
change in pressure. It follows zero order kinetics. The relation may be expressed as:
x
m
= constant
x
m
α P0  P 0 = 1

x
or = K P0
m

iii) At intermediate range of pressure, x/m, will depend upon the power of pressure which lies
between 0 to 1 i.e., fraction power of pressure. This may be expressed as

x x
α p1/n = K.p1/n
m m

 Where n is a constant (whole number) which depends upon the nature of adsorbate and adsorbent.
The constants K and n can be determined as follows:
Taking logarithm on both sides of equation, we get
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x 1
log = logK + logp
m n

 Thus, if we plot a graph between log (x/m) and log p, a straight line will be obtained. Thus slope of

the line is equal to 1/n and the intercept on log (x/m) axis will correspond to log k.

1
x tanθ =
log   n
m θ

log k

log P

x 1
log = logp + logk
m n

[y = mx + C]

LANGMUIR ADSORPTION ISOTHERM:-

The main features of the adsorption theory are as follows:

i) All adsorption sites on the surface of the adsorbent are equivalent and the ability of a particle to
bind itself to a particular site is quite independent of the presence of other sites whether occupied
or not.

ii) The layer of the adsorbed gas is only one molecule thick i.e., it is unimolecular in nature. Since
this type of adsorption is noticed only in case of chemisorption. Langmuir adsorption isotherm
is applied only to chemisorption.

iii) Adsorption process represents two opposing tendencies i.e., condensation (or adsorption) of the
gas molecules on the surface of the solid and evaporation (or desorption) of these molecules back
to the gaseous state.

iv) The rate of condensation of a gas is proportional to the uncovered surface of the adsorbent while
that of evaporation to its covered surface.

 To start with, the entire surface of the solid (adsorbent) is uncovered and the rate of condensation is
very high while that of evaporation is negligible. With the passage of time, more and more of the
surface becomes covered. As a result, the rate of condensation decreases while that of evaporation
increases till the two are equal.1
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Derivation of Expression for Langmuir Adsorption Isotherm:

 Let 1 square centimetre of the surface solid be exposed to a gas maintained at a pressure P. Let at any
instant of the time, the fraction of the surface covered by the adsorbate molecules be q sq. cm.
Therefore, the uncovered surface of the adsorbent will be (1 – θ ) sq. cm.
The rate of condensation α (1 – θ ) = k1 (1 – θ )P The rate of evaporation α θ = k2 θ

At the adsorption equilibrium, Rate of condensation = Rate of evaporation

k1(1 – θ )P = k2 θ or k1P – k1P θ = k2 θ

k 1P
θ  k 2 + k 1P  = k 1Por θ =
(k 2 + k 1P)

Dividing by k2; θ =
 k 2 /k 2P  =
bP
(here b = k1/k2 = constant)
(1 + k 1 /k 2 P) 1 + bp

Now, θ is proportional to x/m i.e. the mass of the gas adsorbed per unit mass of the adsorbent
(solid).
x k bp ap
x/m α θor = k 3θ = 3 =
m 1 + bp 1 + bp

Here, is a constant and is equal to k3b

aP
Thus, x/m = (Langmuir Adsorption Isotherm)
1 + bP

P
Since a and b are constant, a graph between and P must be straight line. The slope is equal to
x/m

‘a’ and intercept on Y-axis is equal to 1/a.

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b
slope ( tan θ ) =
a
θ

 i nte rc e pt c ons ta nt =1 /a

EFFECT OF TEMPERATURE:-
 Mostly adsorption processes are exothermic, therefore the reverse process i.e., desorption is
endothermic.
 If the above equilibrium is subjected to change in temperature then according to Le-chatilier’s
principle, with decrease in temperature adsorption will increase and vice-versa.
 Thus, with increase in temperature at constant pressure the extent of adsorption (x/m)
decrease. However this is true only for physical adsorption.

Physisorption

 In case of chemisorptions the adsorption initially increase with rise in temperature and then
decreases.

Chemisorption

 This behavior is expected because like all chemical reactions some activation energy is required for
chemisorptions.
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 At low temperature, x/m is small. As temperature is increased the molecules of the adsorbate gain
energy and become equal to activation energy so that proper bonds are formed with the adsorbent
molecules.
 Therefore, initially the amount of gas adsorbed increases with rise in temperature. Further increase
of temperature will increase the energy of molecules which have already been adsorbed. This would
increase the rate of desorption and therefore, decrease the extent of desorption.
 The graph between the extent of adsorption and temperature at constant pressure is called
Adsorption isobar.

ADSORPTION FROM SOLUTIONS:-

 Solutes can be adsorbed from solutions by solids e.g:- Cahrcoal adsorbs acetic acid from solution.
 The extent of adsorption decreases with increase in temperature.
 The extent of adsorption increases with increase in surface area of the adsorbent.
 The extent of adsorption depends upon the concentration.

x
= k.C1/n
m

(C is equilibrium concentration)
 The extent of adsorption depends upon the nature of adsorbent and adsorbate.

NOTE:-
 Usually adsorption process is exothermic but some endothermic cases of chemisorption have
also been observed
 Adsorption of H2 on glass surface is spontaneous and endothermic. It involves the change
H 2(g)  2H(g) for which both ΔH and ΔS are positive and because TΔS > ΔH , so ΔG is
negative and the process is spontaneous.
 Adsorption of highly hydrated solutes on solid surfaces is also endothermic. As the molecules
of water of hydration are released during the adsorption, that is why ΔS is positive. To get
ΔG negative TΔS > ΔH
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WORKED OUT EXAMPLES:-

1. 20 grams of charcoal is placed in 100 mL of 0.5 M CH3COOH to form an adsorbed mono

acidic layer of acetic acid molecules and thereby the molarity of acetic acid reduces to 0.49.
The surface area of charcoal is 3×102 m2 g -1 . Find the surface area of charcoal adsorbed
by each molecule of acetic acid.

Sol:- CH3COOH adsorbed = 0.5 -0.49 = 0.01 M

100
Number of molecules adsorbed = 0.01× × 6×1023 = 6×1020
1000

Total area of charcoal = 2× 3×102 = 600m2

600
 Area per molecule = 20
= 1×10-18 m 2
6×10

2. In an experiment 200 mL of 0.5 M oxalic acid is shaken with 10 grams of activated charcoal
and filtered. The concentration of the filtrate is reduced to 0.4 M. Find the amount of
adsorption.

Sol:- Mass of oxalic acid adsorbed by 10 g of charcoal = 200×10-3 (0.5 - 0.4)×90 = 1.8g

(Mol.wt of oxalic acid = 90 g/mol)

The amount of adsorption

x 1.8
 = = 0.18
m 10

3. In the adsorption of acetic acid vapours by 1 gram of charcoal the following data was
obtained:
X (cm3) 0.726 0.478
P (cm of Hg) 0.570 0.210

Determine the value of K and 1/n as used in Freundlich isotherm.

Sol:- According to freudnlich adsorption isotherm

x 1
log = logK + logP
m n

Substituting the values of x. m and p in the equations

0.726 1
log = logK + log0.570 ---------------- (1)
1 n
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0.478 1
log = logK + log0.210 --------------- (2)
1 n

Subtract eq (2) from eq (1)

1
log(0.726 - log0.478) = (log0.570 - log0.210)
n

0.726 1 0.570
log = log
0.478 n 0.210

1 1 0.181
0.181 = (0.434) or = = 0.4170
n n 0.434

In order to calculate the value of K substitute the value of 1/n in equation (1)

log(0.726) = logK + 0.4170 log 0.570

(-0.139) = logK + 0.4170(-0.244)

-
logK = -0.139 + 0.102 = -0.037 = 1.963

-
K = antilog1.963 = 0.9183

4. Which of the following statements is not true.

a) Both physisorption and chemisorptions are exothermic
b) Physisorption takes place with decrease of free energy whereas chemisorptions occurs
with increase of free energy.
c) Physisorption requires low activation energy but chemisorptions requires high
activation energy.
d) The magnitude of chemisorptions increases and that of physisorption decreases with
rise in temperature.

Sol:- (b). For Physisorption and chemisorptions free energy change  G  is negative.

5. The rate of chemisorptions

a) Increases with decrease in temperature
b) Increases with increases in temperature
c) Increases with decrease in the pressure of gas
d) Is independent of pressure of gas

Sol:- (b). Chemisorption involves high activation energy and increases to a maximum value with
rise in temperature.
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6. Which of the He and Ne, gets adsorbed on the surface of charcoal more readily and why?

Sol:- Ne will get adsorbed to more extent because it has large surface area, therefore more vander Waals
forces of attraction. Also it is more easily liquefiable as compared to He. More easily liquefiable
gases are adsorbed to a greater extent.

7. Which of the following statements is wrong?

a) Physical adsorption of a gas is directly related to its critical temperature
b) Chemical adsorption decreases regularly as the temperature is increased
c) Adsorption is an exothermic process
d) A solid with a rough surface is a better adsorbent than the same solid with a smooth
surface.

Sol:- (b).

8. Which of the following is true during adsorption

a) ΔG, ΔH and ΔS are all negative
b) ΔG is negative, but ΔH and S are positive
c) ΔG and ΔH are negative, but S is positive.
d) ΔG and S are positive, but ΔH is positive

Sol:- (a).

CATALYSIS:-

 Catalysis is the phenomenon by which the rate of a reaction is altered ( accelerated or retarded) by
the presence of a substance, which itself remains unchanged chemically at the end in the process.
The substance altering the rate of the reaction is a catalyst.

POSITIVE CATALYSIS:-

 If a catalyst increases the rate of reaction, it is called positive catalyst and the phenomenon is called
catalysis.
 A Positive catalyst increases the rate by lowering the activation energy of reaction.
 Catalyst provides a new pathway of lower activation energy. Consequently, the fraction of the total
number of collisions possessing lower activation energy is increased and hence the rate of reaction
also increases.

EXAMPLES OF POSITIVE CATALYSIS:-

1) 2H 2O2 
Pt
 2H 2O + O2
2) VegetableOil + H2 
Ni
 Ghee
3) CO + 3H2 
Ni
 CH4 + H 2O
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4) 2SO 2 + O 2 
NO
2SO 3

NEGATIVE CATALYSIS:-

 If a catalyst decreases the rate of a reaction, it is called negative catalyst and the phenomenon is
called negative catalysis.

EXAMPLES OF NEGATIVE CATALYSIS:-

1) Addition of small amount of acetanilide (or glycerol or H3PO4)shows slow decomposition of

H2O2.

2) Tetraethyl lead (TEL) acts as an antiknocking agent in the case of petrol. Thus it decreases the
knocking of petrol and acts as a negative catalyst.

3) The oxidation of sodium sulphite by air is retarded by alcohol.

2Na 2SO 3 + O 2 

alcohol
 2Na 2SO4

4) The oxidation of chloroform by air is retarded if some alcohol is added

2CHCl 3 + O 2 
alcohol
 2COCl 2 + 2HCl

AUTO CATALYSIS:-

 In certain reactions one of the products acts as a catalyst. In the initial stage the reaction is slow but
as soon as products are formed, one of the products itself acts as catalyst.

Examples:-

1) When HNO3 is poured on Copper the reaction is very slow in the beginning. Gradually, the
reaction becomes faster due to formation of nitrous acid during the reaction which acts as an auto
catalyst.
2) In the hydrolysis of ethyl acetate, acetic acid and ethyl alcohol are formed. The reaction is
initially very slow but gradually its rate increases. This is due to the formation of acetic acid
which acts as an auto catalyst in this reaction.
CH3COOC2 H5 + H2O  CH3COOH + C2 H5OH

INDUCED CATALYSIS:-

 When one reaction influences the rate of other reaction which does not occur under ordinary
conditions the phenomenon in known as induced catalysis.
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Examples:-

1) Reduction of mercuric chloride (HgCl 2 ) with oxalic acid is very slow but KMnO4 is reduced
readily with oxalic acid. If however, oxalic acid is added to a mixture of KMnO 4 and mercuric
chloride both are reduced are simultaneously. The reduction of KMnO 4 thus induces the
reduction of HgCl2.
2) Sodium arsenite solution is not oxidized by air. If however air is passed through a mixture of the
solution of sodium arsenite and sodium sulphite, both of them undergo simultaneous oxidation.
The oxidation of sodium sulphite thus induces the oxidation of sodium arsenite.

Na3 AsO3 + O2  No Reaction

Na2SO3 + Na3 AsO3 + O2  Na2SO4 + Na3 AsO4

CHARACTERISTICS OF CATALYTIC REACTIONS:

(1) A small quantity of the catalyst is capable of producing the desired effect.

(2) The catalyst does not initiate a reaction; it merely accelerates the reaction that is already
Occurring

(3) The action of a catalyst is specific to a large extent.

(4) The catalyst remains unchanged in amount and chemical composition at the end of the reaction;
It may, however, undergo considerable change in physical form.

(5) A catalyst does not alter the final state of equilibrium in a reversible reaction.A certain minimum

energy must be possessed by the reactants , so that they may react and produce the products,
This is called the activation energy for the reaction. A catalyst is said to lower the activation
energy and thus increase the rate of the reaction.

TYPES OF CATALYSIS:

HOMOGENEOUS CATALYSIS :

 A catalytic process in which the catalyst is in the same phase as the reactant is called homogeneous
catalysis.

Examples:-

2SO2(g) + O2(g)   2SO3(g)

NO
(g)
( Lead -chamber process)

C12 H 22O11 + H 2O   C6 H12O6 + C6 H12O6

+
H (aq)
(Inversion of cane sugar)

HETEROGENEOUS CATALYSIS :
 17

 A catalytic process in which the catalyst and the reactants are in different phases is called
heterogeneous catalysis. This process is also called contact or surface catalysis.

Examples

(I) 2H 2O2(l)   2H 2O(l) + O2(g)

Pt
(s)

(II) 2SO2(g) + O2(g)   2SO3(g)

Pt
(s)

(III) N2(g) + 3H2(g) 

Fe+Mo
 2NH3(g)

(IV) 4NH3(g) + 5O2(g)  

Pt gauze
 4NO(g) + 6H2O(l)

(V) CO(g) + 2H2(g)  

ZnO+Cr2O3
 CH3OH(l)

 The catalytic activity of the catalyst is sometimes improved by the presence of another substance
called promoter.
 The phenomenon of heterogenous catalysis is explained by adsorption theory.
 Adsorption releases energy that decreases the activation energy of reaction. Adsorbed molecules get
activated and atomized and react to give products. Finally products get desorbed and make the
surface available for adsorption of other molecules of reactants.
 Activity of a catalyst depends upon the extent of chemisorption. The ability of a catalyst to direct a
reaction to produce particular products is called selectivity.

Cu/
HCHO
Ni/
CO + H 2 CH 4 + H 2O
ZnO/CuO/Cr2O 3
CH 3OH

Cu/523K/100 atm
CH3OH

CH 4 + O 2
Mo 2O 3 /Δ
H C H O + H 2O

 Heterogenous catalysis some times require a promoter to increase the activity of the catalyst. For
example Mo acts as promoter for Fe in Haber’s process.
 Certain substances are preferentially adsorbed on active sites of catalyst to decrease the activity of a
catalyst. For example As, Co etc. These are called catalytic poisons.
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SHAPE SELECTIVE CATALYSIS:

 When the activity of a catalyst depends on the pore (cavity) size and size of the reactants and
products, the catalysis is called shape selective catalysis.

 The pore size ranges between 260 to 740 pm. Eg:- ZSM -5 is a zeolite (silicate) that acts as shape
selective catalyst to convert methanol to gasoline.

CH3OH 
ZSM-5
-H2O
 CH 2 
polymerisation
 Gasoline
 General formula of zeolites is M x/n (AlO 2 )x (SiO2 )y .mH 2O . Where ‘n’ is valency of metal M.
Eg:- Sodium zeolite (Permutit) - Na2 Al 2Si 2O8 .H2O .

ENZYME CATALYSIS:

 Enzymes are natural protenious bio catalysts that exist in colloidal state.

Eg:- C12 H 22O11 + H 2O 

Invertase
 C6 H12O 6 + C6 H12O 6

C6 H12O 6 
Zymase
2C2 H 5OH + 2CO 2

CHARACTERISTICS OF ENZYMES:

 Enzymes are specific in nature. It is also called lock and key system.

 Enzymes are highly efficient. These increase the rate of reaction minimum to 106 times.

 In human body most of the enzymes are active at 7.4 pH approximately but outside the human body
their optimum activity is at 5 to 7 pH.

 Some times a non protein part called co-enzyme is present with enzyme to increase its efficiency.
Such a part is called apoenzyme and the combination as holoenzyme.

 Generally heavy metal ions poison the activity of enzymes.

MECHANISM OF ENZYME CATALYSIS (LOCK AND KEY SYSTEM):

STEP 1:-

 A fast reaction of binding of substrate ‘S’ on active sites of enzyme ‘E’.

E + S  ES (Complex)

STEP 2:-

 A slow reaction of formation of products from the complex ES is rate determining step.

ES  P + E
(Products)
 19

EXAMPLES OF ENZYME CATALYSIS:

Enzyme Source Enzymetic Reaction

Invertase Yeast Sucrose  Glucose and Fructose
Zymase Yeast Glucose  Ethyl Alcohol and CO2.
Diastase Malt Starch  Maltose
Maltase Yeast Maltose  Glucose
Urease Soyabean Urea  Ammonia and CO2.
Pepsin Stomach Proteins  Amino acids

NOTE:-
 Enzyme lysozyme present in the tears of the eyes protects the surface of the eye from bacterial
infection.

COLLOIDS

 Thomas Graham classified the soluble substances into two categories depending upon their rate of
diffusion through animal and vegetable membranes.

1. Crystalloids: The one having faster rate of diffusion.

2. Colloids: The one having slower rate of diffusion.

CHARACTERISTICS OF COLLOIDS:

1. It is a particular state and not a class of compounds.

2. It is the state in which rate of diffusion through parchment membrane is slow.

3. It is heterogeneous state, i.e., number of phases  2, i.e, each particle is contained within its own
boundaries which separate it form dispersion medium.

4. Thus a colloidal state must have at least two phases. The one phase dispersed in other is known as
dispersed phase (D.P.) or internal phase whereas the other in which dispersions are made is known as
dispersion medium (D.M.) or external phase.

5. It is an intermediate state in between true solution state and suspension state, i.e., particle size of
colloidal state (of dispersed phase) lies in between true solution state and suspension state.

True solution Colloidal state Suspension

Solution + Solvent D.P. + D.M. Precipitate + medium
Size: Solute <10–7 cm DP = 10–5 to 10–7 cm Precipitate = 0.2 to 10–4 cm
 20

6. Particles in a colloidal state are not detectable even under microscope; however, their images can be
noticed in ultra microscope.

7. Colloidal particles do not settle down under the force of gravity even in keeping for long.

8. Colloidal particles always carry charge, +ve or –ve on dispersed phase particles.

DISTINGUISHING FEATURES IN SUSPENSION, COLLOIDS AND TRUE SOLUTIONS

PROPERTY SUSPENSION COLLOID TRUE SOLUTION

Particle size > 10-5 cm or 103 A0 10-7 to 10-5 cm or 10 A0 to < 10-7 cm or 10 A0 or

or 100 μm 103 A0 or 1 mμ to 100 mμ 1 mμ

Visibility Visible with naked Images are visible under Not visible with any of
eye ultra optical microscope. the means

Separation:

a) With filter paper Possible Not possible Not possible

b) With membranes Possible Possible Not possible

Diffusion Does not diffuse Diffuses very slowly Diffuses readily

Setting Settles under Settle under centrifuge Does not settle

influence of gravity

Nature Heterogenous Heterogenous Heterogenous

Appearance Opaque Turbid Clear

CLASSIFICATION OF SOLS BASSED ON INTERACTION BETWEEN D.P. AND D.M.

 Solvent attracting sols are called Lyophilic sols.

 Solvent repelling sols are called Lyophobic sols.

S.No. Property Lyophilic Colloids Lyophobic Colloids

1. Affinity for Very high Quite low or nil
medium
2. Formation Direct mixing of DP and DM Special methods are require
3. Stability Highly self stable Much less stable and require
stabilizers for stability. Easily
coagulated
 21

4. Reversibility Reversible Irreversible

5. Viscocity Higher than DM Equal to that of DM
6. Surface tension Lower than DM Equal to that of DM
7. Electrophoresis Not shown generally Show due to charge on particles
8. Examples Starch, Gelatin, protein sols Sols of metals, As 2S 3 , S 8 , Fe(OH)3

CLASSIFICATION OF SOLS BASSED ON MEDIUM USED

MEDIUM NAME GIVEN TO SOL

Water Aquasol

Alcohol Alcosol

Benzene Benzosol

Air Aerosol

CLASSIFICATION OF COLLOIDS BASSED ON THE PHYSICAL STATE OF D.P. AND D.M.

Disperesed Phase Dispersion Medium Type of colloid Examples

Solid Solid Solid sol Coloured glasses and gem stones
Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter
Liquid Liquid Emulsion Milk
Liquid Gas Aerosol Fog, Mist, Cloud
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap
lather

NOTE:-

 Gas in gas colloids are not possible as gaseous mixtures are true solutions

CLASSIFICATION OF COLLOIDS BASED ON SIZE OF DP AND COLLOIDAL PARTICLES

MACRO MOLECULAR COLLOIDS:-

 The size of DP particles is quite large and have high molecular masses Eg:- starch, gelatin, enzymes,
rubber etc.

MULTI MOLECULAR COLLOIDS:-

 The size of DP particles is less than 1 nm which aggregate to give colloidal particles. Eg:- Gold,
sulphur etc.
 22

ASSOCIATED COLLOIDS OR MICELLES:-

 Some substances act as strong electrolytes but at higher concentrations change into colloids. These
colloids are called associated colloids or micelles.

 Micelles are formed above certain minimum concentration called critical micelle concentration
(CMC) and above a specific temperature called Kraft temperature.

 CMC for soap is 10-4 to 10-3 mol L-1.

 A micelle of soap contain 100 or more RCOO- ions.

 At CMC the non polar long chains of R i.e. hydrophobic tails are pulled inside and polar ends COO -
outside to give ionic micelle.

 Longer and heavier the hydrocarbon chain i.e. hydrophobic character, lesser is the CMC.

+ +
- -
Eg:- CMC of CH 3 (CH 2 )n N(CH 3 )3 Br is less than that of CH 3 (CH 2 )m N(CH 3 )3 Br if n > m.

PREPARATION OF LYOPHILIC SOLS:-

 Lyophilic colloids are very stable an can be prepared by shaking the DP in DM.
Eg:- gelatin, gum, starch etc under hot or cold conditions.

 Sol of cellulose nitrate in ethanol is called collodion.

PREPARATION OF LYOPHOBIC SOLS:-

CONDENSATION METHODS:-

 These methods involve chemical reaction, exchange of solvent, excessive cooling etc.

Br2 + H2S  2HBr + S(Sol) : Oxidation of S2- to S.

2AuCl 3 + 3SnCl 2  2Au(sol) + 3SnCl 4 : Reduction of Au+3 to Au.

FeCl 3 + 3H 2O  Fe(OH)3 (sol) + 3HCl : Hydrolysis of FeCl3.

PorS(solutioninalcohol)+ H2O  Sol of Por S : Exchange of solvent.

PROPERTIES OF COLLOIDAL SOLUTIONS:-

 (a) Nature:- Colloidal solutions are heterogenous.

(b) Colligative properties:- Because of high molecular mass the measured value of colligative
properties is negligible except for osmotic pressure.
(c) Visibility:- particles are visible under Zsigmondy’s ultra microcope.
 23

(d) Colour:- it depends upon the size of particles, eg;- Fine gold colloid is red in colour the colour
changes to blue as the size grows.

(e) Filter ability:- Colloidal particles pass through ordinary filter paper but not through ultrafilters,
animals membrane, cellophone membrane.

(f) Brownian movement:- It is a mechanical property. The zig – zag random motion of colloidal
particles in colloidal solution due to impacts of the particles of dispersion medium is called
Brownian motion.

(g) Tyndall effect:- It is an optical property in which colloidal particles first absorb light and then
scatter at right angle to the direction of the propagation of the light. Visibility of blue colour of sea
water and sky are due to scattering of light by colloidal particles.

(h) Electrophoresis:- It is an electrical property in which charged colloidal particles move towards
the electrodes on application of electric field.

Movement of negatively charged colloidal particles like As2S3, S, Au, Ag, Pt, acid dyes etc towards
anode is called anaphoresis.

Movement of positively charged colloidal particles like Fe(OH) 3, Al(OH)3, Cr(OH)3, Bi, Pb, Fe,
basic dyes etc towards cathode is called cataphoresis.

The pH at which no electrophoresis takes place is called isoelectric point.

STABILITY OF COLLOIDS:-
 Stability is directly proportional to the concentration

 Stability is inversely proportional to the temperature.

 Pressure of some electrolyte to a certain limit stabilizes the colloid.

 Presence of lyophilic sol stabilizes lyophobic sol.

COAGULATION OR FLOCCULATION OR PRECIPITATION:-

 Colloidal particles can be converted to suspended particles by

(a) Addition of oppositely charged colloidal solution that causes the coagulation of both colloids
(b) Continuous electrophoresis
(c) Prolonged dialysis
(d) Addition of suitable electrolyte.

COAGULATION OR FLOCCULATION VALUE:-

 It is the minimum amount of electrolyte in millimoles L-1, of mixed solution needed to coagulate a
colloidal solution.

 Smaller the coagulation value greater is the coagulation power.

 24

 Coagulation values of NaCl, BaCl2 and AlCl3 for As2S3 (-ve sol) are respectively 51 millimoles/lit,
0.69 millimoles/lit and 0.093 millimoles/lit. Their coagulating powers are
1 1 1
i.e., 0.0196(NaCl) > i.e., 1.449 (BaCl2) > i.e., 10.75 (AlCl3).
51 0.69 0.093

1
 Also flocculation value α .
(charge)6

 ± ±2 ±3
Ratio of FLOCCULATION values of M ,M ,M ,M
±4

1 1 1 1
= 6
: 6: 6: 6
(1) (2) (3) (4)

= 1: 0.0156 : 0.00137 : 0.00024

= 100 : 1.56 : 0.137 : 0.024

PROTECTIVE POWER OF LYOPHILIC COLLOID:-

 Lyophilic sols are stable and stabilize lyophobic sols. Such sols are called protective colloids.

 Protective power of a lyophilic sol is inversely proportional to the gold number.

WORKED OUT EXAMPLE:-

(1) For the coagulation of 10 mL of Fe(OH) 3 sol 2 mL of 1 M KBr is required. What is the
flocculation value of KBr.
1
Sol:- 2 mL of 1 M KBr conatins KBr = × 2mol = 2mmol .
1000

Thus 10 mL of Fe(OH)3 sol requires KBr for complete coagulation = 2 mmol.

 1 L i.e. 1000 mL of the solution requires KBr for complete coagulation = 200 mmol.

Hence flocculation value of KBr = 200

HARDY - SCHULZE RULES:-

 Ions having charge opposite to the charge on colloidal particles, coagulate the sol.

 Higher is the charge of coagulating ion, higher is its coagulation power.

 Coagulation power of an electrolyte is directly proportional to the 6 th power of the charge (valency)
of the ion causing coagulation.

EXAMPLES:-

(1) For Fe(OH)3 positive sol, the order of coagulating powers of ions is
 25

-3 -2
[Fe(CN)6 ]4- > PO4 > SO4 > Cl -

(2) For As2S3 negative sol the order of coagulating power of ions is

Sn +4 > Al +3 > Ca +2 > Na +

EMULSIONS:

 Emulsions are colloidal dispersion of one liquid into another liquid (the two liquids should be
immiscible).

 Normally one of the two liquids is water.

 Emulsions are broadly classified into two types:

i) Oil-in water (or o/W)
ii) Water-in-oil (or w/o)

 An oil-in-water emulsion consists of droplets of oil dispersed in water.

 In a water-in-oil emulsions water is present as dispersed phase with oil as the dispersion (or
continuous) medium.

 Which type of emulsion will form on mixing oil and water along with an emulsifying agent will
depend on the composition of the oil and water (usually the liquid with higher percentage becomes
dispersion medium), nature of emulsifying agent (usually water soluble substance stabilize o/w
emulsion whereas oil soluble substance favours the formation of w/o emulsions). The two types of
emulsions are shown in figure.

COMPARISON BETWEEN WATER IN OIL TYPE AND OIL IN WATER TYPE EMULSIONS

Characteristic Water in oil emuslion Oil in water emulsion

Dispersed phase Water Oil
Appearance Oily, opaque and transculent Watery, opaque and transculent
Electrical conductivity Very low Appreciable
Viscocity More than water Little more than water
Dilution test More oil added is soluble but not More water added is soluble but not
 26

water oil
Spreading test Spreads easily on oil surface Spreads easily on water surface
Dye test with oil soluble Dye is soluble giving a bright Dye is practically insoluble
dye colour. Butter, cold creams, coloured droplets are seen. Milk,
benzene water etc are examples cream, face creams are examples

NOTE:-

 Milk is naturally occurring emulsion.

 Argyrol, an eye drop, is silver sol

WORKED OUT EXAMPLES:-

(1) For the coagulation of 100 mL of arsenious sulphite sol 5 mL of 1 M NaCl is required. What is
the flocculation value of NaCl.
1
Sol:- 5 mL of NaCl contains NaCl = × 5mol = 5mmol
1000

Thus 100 mL of As2S3 sol require NaCl for complete coagulation = 5 mmol.

 1 L i.e. 1000 mL of the sol requires NaCl for complete coagulation = 50 mmol

Therefore the flocculation value of NaCl = 50.

(2) The coagulation of 200 mL of a positive colloid took place when 0.73 g HCl was added to
itwithout changing the volume much. Find the flocculation value of HCl for the colloid.
Sol:- 200 mL of the solution requires = 0.73 g of HCl

0.73
Moles of HCl = = 0.02mol = 20mmol
36.5

Therefore 1000 mL (1 lit) of the sol will require

20
= ×1000 = 100mmol
200

(3) 50 mL of standard gold solution needs 0.05 mg of gelatin for its protection from coagulation.
Calculate the gold number of gelatin.
Sol:- 50 mL of standard gold sol requires = 0.05 mg of gelatin

Therefore, 10 mL of standard gold sol requires

0.05
= ×10 = 0.01mg
50

Therefore Gold number = 0.01