DAY TWENTY THREE

Surface
Chemistry
Learning & Revision for the Day
u Adsorption u Colloidal State u Emulsions
u Catalysis u Classification of Colloids

Surface chemistry deals with the phenomenon that occurs at the surface or interfaces. There
are several properties of substances, particularly of solids-liquids and solids-gases, which
depend upon the nature of the surface of interface.

Adsorption
l The accumulation of molecular species at the surface rather than in the bulk of a solid or
liquid is called adsorption.
l The solid substance, on the surface of which adsorption occurs are called adsorbent.
l The molecular species that get adsorbed on the solid surface due to intermolecular
attractions are called adsorbate.
l Rate of adsorption decreases with time whereas rate of absorption remains constant with
time.
l The removal of the adsorbed substance from a surface is called desorption.
l Sorption is a process in which adsorption and absorption take place simultaneously.
e.g. dyes get adsorbed as well as absorbed on the cotton fibres.

Characteristics of Adsorption
Important characteristics of adsorption are as follows :
(i) Adsorption is specific and selective phenomenon, which strictly refers to the existence of
a higher concentration of any particular component at the surface of a liquid or a solid
phase.
(ii) Adsorption is a exothermic process, which accompanied with decrease in free energy of
the system. In adsorption, there is a decrease in entropy of the system.
As, ∆G < 0 and ∆S < 0,
Therefore, ∆H < 0 (Q ∆H = ∆G + T∆S )
Hence, the adsorption is associated with decrease in enthalpy of the system. Thus,
adsorption is always an exothermic process.
(iii) The adsorbed atoms or molecule can be held on the identical conditions. The adsorption of gases on the surface of
surface of a metal by physical forces or chemical forces metals is called occlusion.
due to residual valence bonds.
(iv) All solids adsorb gases to some extent. Adsorption is not 2. Nature of Adsorbate
very pronounced unless an adsorbent possesses a large Generally, the more liquefiable a gas is, the more readily it
surface area for a given mass. Various types of charcoals, will be adsorbed. Easily liquefiable gases such as
silica gels, metal, etc., are used as adsorbents. NH3 , HCl, Cl2 , SO2 , etc., are readily adsorbed than permanent
gases, such as O2 , H2 , N2 etc.
Types of Adsorption 3. Specific Area of Adsorbent
(i) Positive Adsorption If the concentration of an adsorbate at
the surface of adsorbent is more than in the bulk of the It is defined as the surface area of adsorbent available for
adjoining phases, it is called positive adsorption. adsorption per gram of the adsorbate. The greater the surface
area of the solid, the larger would be its adsorbing capacity.
(ii) Negative Adsorption If concentration of an adsorbate at
the surface of adsorbent is less than in the bulk of the 4. Pressure of Gas
adjoining phases, it is called negative adsorption.
At a given temperature, the extent of adsorption will increase
(iii) Physisorption and Chemisorption In physisorption, the with the increase of pressure of the gas. The variation of
particles of the adsorbate are held to the surface of the extent of adsorption with pressure at a constant temperature
adsorbent by physical forces such as van der Waals’ forces is called adsorption isotherm at that temperature.
while in chemisorption, the molecules of the adsorbate
are held to the surface of the adsorbate by chemical The two important adsorption isotherms are as follows :
bonds. (i) Freundlich Adsorption Isotherm Freundlich gave the
 x
following relation between extent of adsorption   and
Comparison between Physisorption and Chemisorption
x  m
pressure. = kp1/n
S.No. Physisorption Chemisorption m
1. van der Waals’ forces are very Chemical bonds are quite where, m is the mass of adsorbent and x that of adsorbate.
weak. strong. x
At low pressure, = kp (Q n = 1)
2. It occurs at low temperature. It occurs at high temperature. m
3. Heat of adsorption is low, in the x
Heat of adsorption is high, in At high pressure, = kp° (Q n = α )
range of 20-40 kJ/mol. m
the range of 40-400 kJ/mol.
4. It is reversible process. It is an irreversible process.
5. It is an instantaneous process. It may be rapid or slow. x
x = kp°
1/n m
6. ∆S is always negative. ∆S is positive for m
= kp
x Saturation
endothermic process. m
x pressure, ps
7. In this, multilayer adsorption In this, single layer = kp
m
occurs and thus, adsorbed adsorption occurs. Thus,
p
layer is several molecules thick. adsorbed layer is only
unimolecular in thickness.
n
NOTE • Chemical adsorption in some cases is endothermic. For x
Taking logarithm of the equation = kp1/n gives,
example, adsorption of hydrogen on glass surface and m
adsorption of highly hydrated solutes on solids. x 1
log = log k + log p
• As the particles of the adsorbate are held on surface, ∆H m n
and ∆S both are negative and ∆H > T∆S. This is true in  x
beginning. As adsorption proceeds ∆H decreases and ∆S Graph between log   and log p is a straight line with
 m
increases and ultimately ∆H = T∆S and ∆G = 0. This state is l
called adsorption equilibrium. slope and intercept log k.
n

Factors Affecting Adsorption 1

slope =
of Gases on Solids A
θ n

Adsorption depends upon following number of factors: x

log
m
OA = log k (intercept)
1. Nature of Adsorbent
O
A gas is adsorbed in different amounts on different log p
adsorbents. Hydrogen is strongly adsorbed on nickel surface
while it is weakly adsorbed on alumina surface under Freundlich adsorption isotherm
 (ii) Langmuir Isotherm Freundlich isotherm fails at high Catalysis can be divided into following groups :
pressure and is only for physical adsorption. (i) Homogeneous Catalysis When the reactants and catalyst
Langmuir isotherm is represented as are in same phase, the process is said to be homogeneous
x ap
= (a and b are constants) catalysis.
m 1 + bp NO( g )
x a e.g. 2SO2 (g) + O2 (g) → 2SO3 (g)
At very high pressure, (bp >> 1) = = constant
m b (ii) Heterogeneous Catalysis When the reactants and catalyst
x are in different phase the process is said to be
At very low pressure, (bp << 1) = ap
m heterogeneous catalysis.
x
∴ ∝p Finely
N2(g) + 3H2 (g) → 2NH3 (g)
m divided Fe(s )
Amount of gas adsorbed

(iii) Auto-catalysis The phenomenon in which one of the

products formed during the reaction acts as catalyst for the
B C reaction is known as auto-catalysis.
x
A e.g. 2KMnO 4 + 5H2C2O 4 + 3H2SO 4 →
m
K2SO 4 + 2MnSO 4 + 8H2O + 10CO2
2+
In this reaction, Mn ions act as auto-catalyst.
O Pressure (p) (iv) Induced Catalysis In this type of catalysis, one reaction
Adsorption isotherm between pressure (p ) and influences the rate of other reaction, which does not
amount of gas adsorbed (x/m) occur under ordinary conditions, e.g. the reduction of
l Freundlich adsorption isotherm and Langmuir HgCl2 by oxalic acid is slow but becomes faster if
adsorption isotherm are applicable to adsorptions from reduction is made in mixture of KMnO 4 and HgCl2 ; where
solutions. both are reduced. Reduction of KMnO4 thus induces the
x reduction of HgCl2 .
Freundlich adsorption isotherm, = kC1/ n (n > 1)
m
x aC Promoters and Inhibitors
Langmuir adsorption isotherm, =
m (1 + bC) Promoters are the substances which can increase the
efficiency of a catalyst. These are also known as coenzymes or
Langmuir adsorption isotherm is applicable only to
activators. Inhibitors are the substances which can make the
chemisorption.
catalyst inactive, e.g. Mg2+ acts as activators for many
−
5. Temperature enzymes while C2O2−
4 and F act as inhibitors as they form

Low temperature favours the physical adsorption, but on complex with Mg2+ .
increasing temperature, physical adsorption decreases.
l Whereas in case of chemisorption, x/ m, initially increases Characteristics of Catalysts
with temperature and then decreases. The initial increase
Some important characteristics of catalysts are discussed
is due to the fact that chemisorption requires activation
below:
energy.
 
l They are temporarily involved in a reaction, providing an
l The graph between extent of adsorption  x  and alternative reaction path of lower activation energy than
 m
temperature T is called adsorption isobar. that for the uncatalysed reaction.
l They catalyse both forward and backward reactions to the
p = constant same extent in a reversible reaction and thus have no
x x effect on the equilibrium constant.
m p = constant m
l The catalyst remains unchanged in amount and chemical
composition at the end of the reaction. It may undergo
some physical change.
T T
l Only a small quantity of the catalyst is generally needed.
One mole of colloidal platinum in 10 8 L can catalyse
Catalysis decomposition of H2O2 .
l In certain reactions, the rate of the reaction is dependent
A substance that can influence the rate of a chemical reaction
on the concentration of the catalyst. e.g. Rate of inversion
but is not consumed during the reaction is known as catalyst.
of cane sugar is dependent on the concentration of H+
The catalyst change the rate of reaction by providing an
used as catalyst.
alternate path of different activation energy. This
phenomenon is known as catalysis.
 Rate of the reaction in certain heterogeneous reaction
l

varies with surface area of the catalyst. Hence, finely

Colloidal State
divided metals are preferred in the form of catalyst. A substance is said to be in the colloidal state, when it is
l The catalyst does not initiate the reaction and are specific in dispersed in another medium in form of very small particles
their action, e.g. starting from H2 and CO, 3 different having diameter between 10 −9 m to 10 −6 m.
products are possible using different catalysts as
Ni Distinction between True Solutions,
CO (g) + 3H2 (g) → CH4 (g) + H2O (g)
Colloidal Solutions and Suspensions
Cu /ZnO- Cr2O3
CO (g) + 2H2 (g) → CH3OH (g) Depending upon the size of the particles, there are three
Cu different types of solutions viz, true solutions, suspensions
CO (g) + H2 (g) → HCHO and colloidal solutions.
250 °C

Activity and Selectivity of Catalyst Properties

True solutions Colloidal
Suspensions
solutions
l Activity is the ability of catalysts to accelerate chemical (Molecular
(Colloidal (Coarse dispersion)
reactions. solutions) disperison)
l Activity of catalyst depends upon the strength of Size Less than 1 nm Between 1 nm Greater than
chemisorption to a large extent. or 10 −7 cm and 1000 nm or 1000 nm or 10 −4 cm
l Selectivity means a given substance can act as catalyst 10 −7- 10 −4 cm
only in a particular reaction and not for all reactions. e.g. Visibility Invisible even Visible only Visible even by
Ni under ultra- under ultra- naked eye
(i) CO(g) + 3H2 (g) → CH4 (g) + H2O(g) microscope microscope
Cu
(ii) CO(g) + H2 (g) → HCHO(g) Diffusion Diffuse readily Diffuse slowly No diffusion
through through
Cu /ZnO −Cr 2O3
(iii) CO(g) + 2H2 (g) → CH3OH (g) parchment parchment
membrane membrane
Filtration Possible Possible Impossible through
Enzyme Catalysis through filter through filter filter paper and
paper and paper but not parchment
l Enzymes are biochemical catalysts. They are proteins and parchment through membrane
extremely specific in nature. membrane parchment
Urease membrane
e.g. NH2CONH2 + H2O → 2NH3 + 2CO2
Scattering No scattering Scattering takes Do not show
l Common steps for all enzyme catalysed reactions are of light place (Tyndall Tyndall effect
(i) E + S q ES (fast, reversible) effect)

(ii) ES → E + P (slow, rate determining) Settling Do not settle Do not settle but Settle under gravity
settle when at normal condition
Some important reactions involving enzymes are given below centrifuged
in table :
Nature Homogeneous Heterogeneous Heterogeneous
Reaction Catalyst Brownian Do not show Show May show
C 12 H 22O11+ H 2O → C 6 H12O 6 +C 6 H12O 6 Invertase motion
Sucrose Glucose Fructose
Appearance Clear Generally clear Opaque
C 12 H12O11 + H 2O → 2C 6 H12O 6 Maltase or opaque
Maltose Glucose

2 (C 6 H10O 5 )n + nH 2O → n(C 12 H 22O11 ) Diastase Dispersed Phase and Dispersion Medium

Starch Maltose
The colloidal system is made of two phases :
C 6 H12O 6 → 2C 2 H 5OH + CO 2(g) Zymase
Glucose Ethanol l The substance distributed as the colloidal particles, called
the dispersed phase.
NH 2 CONH 2 + H 2O → 2NH 3 + CO 2 (l) Urease
Urea l The phase in which the colloidal particles are scattered,
+
CO 2(aq ) + H 2O q H ( aq ) + HCO −3 ( aq ) Carbonic anhydrase called dispersion medium.
(in human body)
The dispersed phase or dispersion medium can be a gas,
N 2 (atmospheric) → NH 3 Nitrogenase liquid or solid. There are eight types of colloidal system.
 (ii) Macromolecular colloids are the colloids in which colloidal
Classification of Colloids particles themselves are large molecules.
Colloids can be classified in a number of ways based upon (iii) Associated colloids or micelles are the substances which
some of their important characteristics as given below: behave as normal electrolytes at low concentration but as
colloids at higher concentration. This is because at higher
1. Based upon Appearance concentration, they form associated particles called
On this basis, colloids can be classified into eight classes. micelles, e.g. soap and synthetic detergents.
These are as follows: The concentration above which micelle formation occurs,
Colloidal Dispersed Dispersion is called CMC (critical micelle concentration) and the
Examples temperature above which micelle formation occurs is
system phase medium
Foam Gas Liquid Soda water, froth, called Kraft temperature.
shaving cream The colligative properties of colloidal systems are low due
Solid foam Gas Solid Foam rubber, cork to aggregation. Hence, all colloidal solutions exhibit very
low osmotic pressure, very small elevation in boiling point
Aerosol Liquid Gas Fog, mist, clouds
and depression in freezing point.
Emulsion Liquid Liquid Milk, hair cream
Solid emulsion Liquid Solid Butter, cheese
(gel) Preparation of Lyophobic Solution
Aerosol of solids Solid Gas Dust in air, smoke Lyophilic colloids may be prepared by simply warming the
Sol Solid Liquid Paint, ink, colloidal solid with the liquid dispersion medium. On the other hand,
gold, lyophobic colloids have to be prepared by special methods.
Solid sol Solid Solid Ruby glass, some Substances are converted into colloidal solutions by the two
gem stones, methods.
alloys, rock salt l Dispersion methods involve the breaking of bigger
particles to the size of colloidal particles. The various
2. Based Upon Charge dispersion methods are :
The colloids can be classified into positive or negative (i) Electro-disintegration method (Bredig’s arc method)
colloids according to the charge present on the dispersed By this method, colloidal solutions of metals like gold,
phase particles. silver etc., are obtained.
(ii) Peptisation : e.g.
3. Lyophilic and Lyophobic Colloids
Fe(OH)3 + FeCl3 → [Fe(OH)3 Fe]3+ + 3Cl−
On this basis of affinity with solvent, colloids can be Fresh ppt. Electrolyte Colloid
classified into following two types. l Condensation methods involve the growing of size of the
(i) Lyophilic colloids represent such colloidal systems in dispersed phase or the size of colloidal particles.
which the particles of dispersed phase have great affinity (i) By double decomposition
for the dispersion medium. These are reversible colloids,
As2O3 + 3H2S → As2S3 + 3H2O
e.g. gum, gelatin, rubber, proteins etc. Colloidal solution
(ii) Lyophobic colloids represent such colloidal systems in (ii) By hydrolysis
which particles of the dispersed phase have no affinity for FeCl3 + 3H2O → Fe(OH)3 + 3HCl
the dispersion medium. These are irreversible, e.g. sols Colloidal solution
of metals and their insoluble compounds like sulphides (iii) By oxidation
and oxides. Lyophobic colloids are less stable due to
H2S+ 2HNO3 → 2H2O + 2NO2 + S
the presence of electric charge on their particles. Colloidal
If water is the dispersion medium, the terms used are
hydrophilic and hydrophobic colloids. On the Purification of Colloidal Solutions
otherhand, lyophilic colloids are stable due to their The following methods are commonly used to purify the
presence of charge as well as their extensive solvation. colloids.
4. Based on Molecular Size (i) Dialysis It is the process of removing small molecules
or ions from a colloidal sol by diffusion through a
On this basis, colloids are classified into three types : semipermeable membrane. In this process, impure
(i) Multimolecular colloids are the colloids in which colloidal solution is placed in a bag of semipermeable
colloidal particles consist of aggregate of atoms or membrane, dipping in water, the ions diffuse through
small molecules with diameter less than 10 −9 m or membrane. Ferric hydroxide sol can be purified by this
1 nm, e.g. a sol of gold, a sol of sulphur. method.
 (ii) Electrodialysis If dialysis is carried out under the influence Out of the above methods, the last one is most common and
of electric field, it is called electrodialysis. This speeds up the governed by Hardy-Schulze rule.
migration of ions to the opposite electrodes. (i) According to this rule, Higher the valency of the active
(iii) Ultrafiltration Separation of sol particles from the liquid ion, the greater will be its power to precipitate the sol. e.g.
medium and electrolytes by filtration through an order of coagulating power is
ultrafilter is called ultrafiltration. Al3+ > Ba2+ > Na+ for negative solution
(iv) Ultra-centrifugation In ultra-centrifuge, the colloidal PO34− > SO24− > Cl− for positive solution
particles settle down at the bottom and impurities remain
in the solution. (ii) Protective Action As lyophobic sols are unstable (e.g. Au,
Ag) and get easily precipitated, the addition of lyophilic
Properties of Colloidal Solutions colloids like gums, soaps etc., makes it difficult. The
The important properties of the colloidal solutions are given process is known as protection and the lyophilic colloids
below: are termed as protective colloids.
(i) Brownian Movement Colloidal particles are always in a (iii) Gold Number It is the minimum weight (in mg) which
state of rapid random motion, which is termed as must be added to 10 mL of given gold sol, so that no
Brownian movement. coagulation of it takes place when 1 mL of 10% NaCl
(ii) Tyndall Effect When a strong and converging beam of solution is rapidly added to it.
light is passed through a colloidal solution, its path
becomes visible due to scattering of light by particles. It is Emulsions
called Tyndall effect. These are the colloidal solutions of two immiscible liquids in
(iii) Electrophoresis The phenomenon, involving the migration which the liquids act as the dispersed phase as well as the
of colloidal particles under the influence of electric field dispersion medium.
towards the oppositely charged electrode, is called
electrophoresis. Sedimentation potential or Dorn effect is
the reverse of electrophoresis and set up when a particle
Types of Emulsions
is forced to move in a resting liquid. There are two types of emulsions :
(iv) Coagulation or Flocculation The precipitation of particles (i) Oil in water type, in which tiny droplets of liquid fat are
of the dispersed phase in a sol is known as coagulation. dispersed in water. e.g. milk
The minimum amount of an electrolyte required to cause (ii) Water in oil type, in which water being dispersed in
precipitation of one litre of a colloidal solution is called lubricating oil. e.g. stiff greases
coagulation value or flocculation value. The reciprocal of l
Emulsifying Agents During the preparation of
coagulation value is regarded as the coagulating power. emulsion, a small amount of some substances such as
Coagulation can be achieved by following means, soap, gum, agar and protein etc., are added to stabilise
(a) electrophoresis the emulsion. These substances are known as
emulsifying agents.
(b) mixing two oppositely charged sol
(c) boiling
l
Breaking of Emulsions Emulsions can be broken into
(d) addition of electrolytes, etc. constituent liquids by heating, freezing, centrifuging or
chemical destruction of emulsifying agent.
DAY TWENTY THREE SURFACE CHEMISTRY 247

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 Adsorbed acetic acid on activated charcoal is (c) the heat of adsorption varies with coverage
(a) adsorber (b) adsorbent (c) adsorbate (d) absorber (d) the adsorbed molecules interact with each other
2 Which of the following is not applicable to the 9 At high pressure, Langmuir adsorption isotherm takes
phenomenon of adsorption? the form
(a) ∆H > 0 (b) ∆G < 0 (c) ∆S < 0 (d) ∆H < 0 (a)
x
=
ap
(b)
x a
=
m 1 + bp m b
3 Which one of the following characteristics is associated
x m b 1
with adsorption? ª NEET 2016, Phase I (c) = ap (d) = +
m x a ap
(a) ∆G, ∆H and ∆S all are negative
(b) ∆G and ∆H are negative but ∆S is positive 10 In Freundlich adsorption isotherm, the value of 1/n is
(c) ∆G and ∆S are negative but ∆H is positive ª CBSE-AIPMT 2012
(d) ∆G is negative but ∆H and ∆S are positive (a) between 0 and 1 in all cases
4 Which of the following statements is correct for the (b) between 2 and 4 in all cases
spontaneous adsorption of a gas? ª CBSE-AIPMT 2014 (c) 1 in case of physical adsorption
(d) 1 in case of chemisorption
(a) ∆S is negative and therefore, ∆H should be highly
positive 11 If x is amount of adsorbate and m is amount of
(b) ∆S is negative and therefore, ∆H should be highly adsorbent, which of the following relations is not related
negative to adsorption process? ª CBSE-AIPMT 2011
(b) p = f (T ) at constant  
(c) ∆S is positive and therefore, ∆H should be negative x x
(a) = f (T ) at constant p
m m
(d) ∆S is positive and therefore, ∆H should also be highly
x x
positive (c) = p ×T (d) = f (p) at constantT
m m
5 Adsorption in multilayer, occurs in case of
(a) physical adsorption (b) chemical adsorption
12 Which one of the following is an example for
(c) Both (a) and (b) (d) None of these homogeneous catalysis?
(a) Manufacture of sulphuric acid by contact process
6 Which one of the following characteristics is not correct (b) Manufacture of ammonia by Haber’s process
for physical adsorption? (c) Hydrolysis of sucrose in presence of dilute hydrochloric
(a) Adsorption on solids is reversible acid
(b) Adsorption increases with increase in temperature (d) Hydrogenation of oil
(c) Adsorption is spontaneous
(d) Both enthalpy and entropy of adsorption are negative 13 Which of the following process does not occur at the
interface of phases?
7 Which one of the following graphs represents Freundlich
(a) Crystallisation (b) Heterogeneous catalysis
adsorption isotherm? (c) Homogeneous catalysis (d) Corrosion
14 In which of the following reactions heterogeneous
x. x. catalysis involved?
(a) log (b) log
m m
NO ( g )
I. 2SO 2 (g) + O 2 (g) → 2 SO3 (g)
log p log p
Pt (s )
II. 2SO 2 (g) + O 2 (g) → 2 SO3 (g)
Fe (s )
(c) log
x.
(d) log
x. III.N2 (g) + 3 H2 (g) → 2NH3 (g)
m m
HCl (l )
l + H2O ()
IV.CH3COOCH3 () l → CH3COOH (aq) + CH3OH (aq)
log p log k
(a) II and III (b) II, III and IV (c) I, II and III (d) Only IV
8 The Langmuir adsorption isotherm is deduced using the 15 Which of the following reactions is an example of
assumption heterogeneous catalysis?
Cl
(a) the adsorption takes place is monolayer (a) O 3 + O → 2O 2 (gas phase)
(b) the adsorption sites are equivalent in their ability to NO
adsorb the particles (b) 2CO(g) + O 2 (g) → 2CO 2 (g)
 O 24 Lyophilic colloids are stable due to

(c) CH3  C  OC 2H5 ()
l + H2O()
l (a) charge on particles
O (b) large size of the particle
 (c) small size of the particles
H 2SO 4
→ CH3 C  OH ()
l + C 2H5OH ()
l (d) layer of dispersion medium on the particles
Cu, ZnO -Cr 2O 3
(d) CO (g) + 2H2 (g) → CH3OH ()
l 25 Which of the following is not correct?
(a) Milk is a naturally occurring emulsion
16 According to the adsorption theory of catalysis, the (b) Gold sol is a lyophilic sol
speed of reaction increases because (c) Physical adsorption decreases with rise in temperature
(a) adsorption lowers the activation energy of the reaction (d) Chemical adsorption is unilayered
(b) the concentration of reactant molecules at the active 26 The Brownian motion is due to
centres of the catalyst becomes high due to adsorption
(a) temperature fluctuation within the liquid phase
(c) in the process of adsorption, the activation energy of the
(b) attraction and repulsion between charges on the
molecules becomes large
colloidal particles
(d) adsorption produces heat, which increases the speed (c) impact of the molecules of the dispersion medium
of the reaction (d) convectional currents
17 The efficiency of enzyme catalysis is due to its capacity 27 Tyndall effect is more pronounced in
to
(a)hydrophilic sols (b) hydrophobic sols
(a) form a strong enzyme-substrate complex (c)lyophilic sols (d) Both (a) and (b)
(b) change the shape of the substrate
(c) lower the activation energy of the reaction 28 Blood may be purified by
(d) form a colloidal solution in water (a) dialysis (b) electro-osmosis
(c) coagulation (d) filtration
18 The enzyme which can catalyse the conversion of
glucose to ethanol is 29 Which of the following process is responsible for the
(a) zymase (b) invertase (c) maltase (d) diastase formation of delta at a place where rivers meet the sea?
(a) Emulsification (b) Colloid formation
19 Colloidal solution of gold prepared by different methods
(c) Coagulation (d) Peptisation
are of different colours because of
(a) variable valency of gold 30 Which of the following electrolytes is least effective in
(b) different concentrations of gold particles coagulating ferric hydroxide solution?
(c) impurities produced by different methods (a) KBr (b) K 2 SO 4
(d) different diameters of colloidal gold particles (c) K 2CrO 4 (d) K 4 [Fe(CN)6 ]
20 Which one of the following statements is incorrect about 31 On which of the following properties does the
enzyme catalysis? ª CBSE-AIPMT 2012 coagulating power of an ion depend? ª NEET 2018
(a) Enzymes are mostly proteinous in nature (a) Both magnitude and sign of the charge on the ion
(b) Enzyme action is specific (b) Size of the ion alone
(c) Enzymes are denaturated by UV-rays and at high (c) The magnitude of the charge on the ion alone
temperature (d) The sign of charge on the ion alone
(d) Enzymes are least reactive at optimum temperature 32 The concentration of electrolyte required to coagulate a
21 Fog is a colloidal solution of ª NEET 2016, Phase I given amount of As 2S 3 sol is minimum in case of
(a) Gas in liquid (b) Solid in gas (a) K 2SO 4 (b) Al(NO 3 )3 (c) Mg(NO 3 )2 (d) KNO 3
(c) Gas in gas (d) Liquid in gas 33 Which is more powerful to coagulate the negative
22 Which one of the following forms micelles in aqueous colloid?
solution above certain concentration? (a) ZnSO 4 (b) Na 3PO 4 (c) AlCl 3 (d) K 4 [Fe(CN)6 ]
(a) Urea 34 The coagulation values of AlCl 3 and NaCl are 0.093 and
(b) Dodecyl trimethyl ammonium chloride 52 respectively. The ratio of coagulating power of both
(c) Pyridinium chloride will be
(d) Glucose (a) 0.093 : 1 (b) 52 : 1 (c) 559 : 1 (d) 1.788 : 1
23 Which of the following forms cationic micelles above 35 Alum helps in purifying water by
certain concentrations? (a) forming Si complex with dirt particles
(a) Sodium ethyl sulphate (b) sulphate part which combines with dirt and removes it
(b) Sodium acetate (c) making mud water soluble
(c) Urea
(d) aluminium ions which coagulates the mud particle
(d) Cetyltrimethyl ammonium bromide
36 Bleeding due to a cut can be stopped by applying ferric The protective nature of these colloidal solutions follow the order
chloride solution in the laboratory. This is due to (a) C > B > A (b) A > B > C
(a) coagulation of negatively charged blood particles by (c) A = B = C (d) B > A > C
Fe 3+ ions 39 Milk is
(b) coagulation of positively charged blood particles by Cl − ions (a) fat dispersed in water (b) fat dispersed in milk
(c) reaction taking place between ferric ions and the (c) fat dispersed in fat (d) water dispersed in milk
haemoglobin forming a complex 40 Which of the following substances will precipitate the
(d) common element, iron, in both FeCl 3 and haemoglobin negatively charged emulsions?
37 The protecting power of lyophilic colloidal sol is I. KCI II. glucose III. urea IV. NaCl
expressed in terms of ª CBSE-AIPMT 2012 The correct answer is
(a) coagulation value (b) gold number (a) I and II (b) I and III (c) I and IV (d) II and III
(c) critical micelle concentration (d) oxidation number
41 An emulsion cannot be broken by……and……
38 The gold numbers of some colloidal solutions are given I. heating
below: II. adding more amount of dispersion medium
Colloidal solution Gold number III. freezing
A 0.01 IV. adding emulsifying agent
B 2.5 The correct answer is
C 20 (a) I and II (b) II and III (c) II and IV (d) I, II and III

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1 Plot of log x/m against log p is a straight line inclined at 5 Adsorption is accompanied by the evolution of heat, so
an angle of 45°. When the pressure is 0.5 atm and according to Le-Chatelier’s principle, the amount of
Freundlich parameter k is 10, the amount of solute substance adsorb with temperature as
adsorbed per gram of adsorbent will be (log 5 = 0.6990) (a) increases with decrease inT
(a) 1 g (b) 2 g (c) 3 g (d) 5 g (b) increases with increase inT
(c) decreases with decrease inT
2 On adding 1 mL of solution of 10% NaCl to 10 mL of gold
(d) None of the above
sol in the presence of 0.25 g of starch, the coagulation is
just prevented. The gold number of starch is 6 For the following reaction,
(a) 0.25 (b) 0.025 (c) 25 (d) 250 C 6H12O6(aq) + H2 (g) -
C 6H14O6(g)
−4
3 The density of gold is 19 g/cm . If 1.9 × 10 3
g of gold is Which one of the following is not affected by the
dispersed in 1 L of water to give a sol having spherical addition of catalyst?
gold particles of radius 10 nm, then the number of gold (a) Rate of forward reaction
particles per mm 3 of the sol will be (b) Rate of backward reaction
(a) 1.9 × 1012 (b) 6.3 × 1014 (c) 6.3 × 1010 (d) 2.4 × 106 (c) Time required to reach the equilibrium
(d) Spontaneity
4 In homogeneous catalytic reactions, there are three
alternative paths A, B and C (shown in the figure). Which 7 Which among the following statements are correct with
one among the following option indicates the relative respect to adsorption of gases on a solid?
ease with which the reaction can take place?
I. The extent of adsorption is equal to kp n according
A
to Freundlich isotherm.
Potential energy →

B
II. The extent of adsorption is equal to kp 1/ n
C
according to Freundlich isotherm.
 1 + bp 
III. The extent of adsorption is equal to  
according to Langmuir isotherm  ap 
ap
IV. The extent of adsorption is equal to
(1 + bp)
according to Langmuir isotherm
Reaction coordinate →
(a) A > B > C (b) C > B > A (a) I and II (b) I and IV
(c) B > C > A (d) A = B = C (c) II and III (d) II and IV
 8 Which of the following factors are responsible for the 11 If a freshly formed ppt. of SnO2 is peptised by a small
increase in the rate of surface catalysed reaction? amount of NaOH, these colloidal particles may be
represented as
I. A catalyst provides proper orientation for the
(a) [SnO2 ] SnO32– : 2Na + (b) [SnO2 ] Sn4 + : O2–
molecules to react.
(c) [SnO2 ] Na + : OH− (d) [SnO2 ] Sn4+ : OH−
II. Heat of adsorption of reactants on a catalyst, helps
reactant molecules to overcome activation energy. 12 [AgI] I– colloidal sol can be coagulated by the addition of
a suitable cation. 1 mol of [AgI] I − requires mol of
III. The catalyst increases the activation energy of the AgNO3, Pb(NO3 )2 and Fe(NO3 )3 as
reaction.
(a) 1, 1, 1 (b) 1, 2, 3
IV. Adsorption increases the local concentration of 1 1
(c) 1, , (d) 6, 3, 2
reactant molecules on the surface of the catalyst. 2 3
Select the correct answer using the codes given 13 50 mL of 1M oxalic acid is shaken with 0.5g wood
below: charcoal. The final concentration of the solution after
(a) I and II (b) I and II (c) I, II and IV (d) I and III adsorption is 0.5 M. What is the amount of oxalic acid
9 Which one of the following reactions is an example of absorbed per gram of carbon?
auto-catalysis? (a) 3.45g (b) 6.30 g
(a) 2As H3 (g) → 2As(g) + 3H2 (g) (c) 3.15g (d) None of these
(b) N2 (g) + 3 H2 (g) Fe(
 s)
→ 2NH3 (g) 14 The gold number of gelatin, haemoglobin, and sodium
NO( g )
(c) 2 SO2 (g) + O2 (g)  → 2SO3 (g) acetate are 0.005,0.05 and 0.7 respectively. The
+
l + H2O()
(d) C12H22O11 () l H→ C6 H12O6 ()
l + C6H12O6 ()
l protective actions will be in the order of
(a) gelatin < haemolgobin < sodium acetate
10 Graph between log   and
x
(b) gelatin > haemoglobin > sodium acetate
 m
(c) haemoglobin > gelatin >sodium acetate
log p is a straight line at angle (d) sodium acetate > gelatin > haemoglobin
45° with intercept OA as 45°
x A 15 The volume of a colloidal particle,Vc as compared to the
shown. Hence,   at a x volume of a solute particle in a true solutionVs , could be
 m log
m 0.3010
Vc Vc
pressure of 0.2 atm is (a) ≈ 103 (b) ≈ 1023
Vs Vs
O log p V V
(a) 0. 2 (b) 0. 4 (c) c ≈ 10− 3 (d) c ≈ 1
(c) 0. 6 (d) 0. 8 Vs Vs

ANSWERS
SESSION 1 1. (c) 2. (a) 3. (a) 4. (b) 5. (a) 6. (b) 7. (c) 8. (a) 9. (b) 10. (a)
11. (c) 12. (c) 13. (c) 14. (a) 15. (d) 16. (a) 17. (c) 18. (a) 19. (d) 20. (d)
21. (d) 22. (b) 23. (d) 24. (d) 25. (b) 26. (c) 27. (b) 28. (a) 29. (c) 30. (a)
31. (a) 32. (b) 33. (c) 34. (c) 35. (d) 36. (a) 37. (b) 38. (b) 39. (a) 40. (c)
41. (c)

SESSION 2 1. (d) 2. (d) 3. (d) 4. (b) 5. (a) 6. (d) 7. (d) 8. (c) 9. (a) 10. (b)
11. (a) 12. (c) 13. (b) 14. (b) 15. (a)
DAY TWENTY THREE SURFACE CHEMISTRY 251

Hints and Explanations

SESSION 1 (ii) Adsorption consists of two opposing Pt ( s)
(ii)2SO 2 (g ) → 2SO 3 (g )
processes condensation and
1 Adsorbed acetic acid on charcoal is evaporation. Here, reactant SO 2 and product SO 3
called adsorbate.
(iii) The rate of condensation depend are in gaseous phase while platinum
2 For adsorption, the value of ∆ H should is in solid phase. So, this reaction
upon the uncovered surface of the
not be greater than 0. adsorbent available for represents a heterogeneous
3 Adsorption is a spontaneous process condensation. catalysis.
that occurs with release in energy and Fe ( s)
decrease in the randomness
9 Langmuir adsorption isotherm is (iii)N2 (g ) + 3H2 (g ) → 2NH3 (g )
x ap
(i.e. entropy) of the adsorbed substance. = Similarly, here N2 and H2 reactants
m 1 + bp
For a spontaneous process, ∆G must are in gaseous phase, while Fe is in
be negative. At higher pressure, 1 + bp = bp solid phase. Whereas in other
∆G = ∆H − T∆S x ap a reactions catalyst is in same phase
= =
As the process is exothermic and m bp b with reactant(s) and product(s).
randomness of molecule (entropy) 10 In Freundlich adsorption isotherm, Cu, ZnO, Cr O ( s)
decreases hence, both ∆H and ∆S will
15 CO(g ) + 2H2 (g ) →
2 3
CH3OH(l )
x
be negative as well. = kp1/ n In this reaction, reactant and catalyst are
m
4 ∆S [change in entropy] and ∆ H [change in different phase, hence it is an example
The value of n is always greater than 1. of heterogeneous catalysis.
in enthalpy] are related by the equation,
So, the value of 1/ n lies between 0 and 1
∆G = ∆ H − T∆S [Here, ∆G = change in 16 In heterogeneous catalysis, adsorption
in all cases.
Gibbs free energy] lowers the activation energy of the
x
For adsorption of a gas, ∆S is negative 11 = p × T is the incorrect relation. reaction.
m
because randomness decreases. Thus, x p 17 The efficiency of enzyme catalysis is
in order to make ∆G negative [for The correct relation is ∝ .
m T due to its capacity to lower the
spontaneous reaction], ∆H must be activation energy of the reaction.
highly negative because reaction is 12 In homogeneous catalysis, reactants Enzymes are biocatalysts which
exothermic. Hence, for the adsorption and catalyst are in the same phase. increases the rate of reaction without
of a gas, if ∆S is negative, then ∆H Pt ( s ) being consumed in the reaction. In
should be highly negative. (a)SO 2 (g ) + O 2 (g ) q SO 3 (g ) It is an
(Contact process)
case of equilibrium reactions, catalysts
5 Physical adsorption involves multilayer help in attaining the equilibrium quickly
example of heterogeneous catalysis.
adsorption. without disturbing the equilibrium.
Fe ( s)
6 Extent of adsorption decreases with (b)N2 (g ) + H2 (g ) q 2 NH3 (g ) It is an Zymase
increase in temperature. (Haber’s process) 18 C 6H12O 6 → 2C 2H5OH + 2CO2
Glucose Ethanol
example of heterogeneous catalysis.
7 When we plot a graph between log( x / m) HCl ( aq ) 19 Colour of colloidal sol depends upon the
and log p, a straight line with positive (c)C12H22O11(aq ) + H2O(aq ) q
size of colloidal gold particles.
slope is obtained. This graph represents C 6H12O 6 + C 6H12O 6
the Freundlich adsorption isotherm. 20 Most of the enzymes have proteinous
It is an example of homogeneous
nature. They are highly specific and get
catalysis.
1 denaturated by high temperature or
slope n
(Hardening)
(d) Oil (l ) + H2 (g ) → Fat UV-rays. At optimum temperature,
Pt ( s)
x. which is generally in between 25°-35°C,
log
m It is also an example of enzyme activity is maximum.
intercept = log k heterogeneous catalysis. 21 Fog is a colloidal solution of liquid in a
13 Homogeneous catalysis does not occur gas, in which liquid is the dispersed
log p
at the interface of phases as in case of phase whereas gas is the dispersion
Graph of Freundlich adsorption isotherm homogeneous catalysis, reactant and medium. Examples of other options are
catalyst have same phase and their as follows:
8 Main points of Langmuir theory of
adsorption are: distribution is uniform throughout. Gas in liquid : Shaving cream, soda
water, froth
(i) Adsorption takes place on the 14 (i) Reaction in which catalyst is in
Solid in gas : Dust in air
surface of solid only till the whole of different phase than other (reactants
and products) is known as Gas in gas : Atmospheric air.
the surface is completely covered
with a unimolecular layer of the heterogeneous catalysis.
adsorbed gas.
22 Surfactants detergents form micelles in Coagulating power of an ion depends 37 Lyophobic sols are unstable, so they
aqueous solution above their CMC. both on magnitude and sign of the are stabilised by adding some lyophilic
Dodecyl trimethyl ammonium chloride charge (positive or negative) on the ion. colloids which protect them from
is an example of surfactant, so it This fact can be explained by precipitation. Thus, lyophilic colloids
shows a the given phenomenon. Hardy-Schulze rule. are called protecting colloids. Their
CH3 According to this rule “greater the protecting power is expressed in terms
+ valency of the coagulating of gold number.
CH3 (CH2 ) 11  N  CH3 ion/flocculating ion (oppositely charged Note Lesser the gold number, higher is
Cl −
1442443
Non -polar part ion) added, the greater is its power to the protecting power.
CH3
14 42443 cause coagulation.
Polar part
To coagulate a positively charged sol, 38 Smaller the value of gold number,
(Dodecyl trimethyl ammonium chloride) the order of coagulating power of greater will be the protecting power of
negative ion is the protective colloid.
23 Cetyltrimethyl ammonium bromide
Hence, protective nature of A, B and C as
forms cationic micelles above a certain I− < SO 24 − < PO 34 − < [Fe(CN)6 ]4 − .
concentration. Colloidal solution A > B > C
Similarly, to coagulate a negatively
24 Lyophilic colloids are stable due to layer charged sol, the order of coagulating Gold number 0.01 2.5 20
of dispersion medium on the particles. power of positive ions is
39 Milk is an emulsion in which the particles
25 Gold sol is a lyophobic sol, instead of a Ag+ < Pb 2+ < Fe 3+ < Si 4+ (or globules) of liquid fats are dispersed
lyophilic sol. All other given statements 3+ in water.
32 As 2S3 is a negatively charged sol. Al
are correct. 40 The droplets present in emulsion has
ions from Al(NO 3 )3 will be most effective
26 Brownian motion is the random negative charge. It can be precipitated
for bringing the coagulation.
movement of the low weight particles by adding electrolyte such as KCl, NaCl
suspended in a fluid. It arises because 33 Negative colloid is coagulated by etc. Since, glucose and urea do not
positive ion or vice-versa. Greater the produce ions on dissolving in water.
of the unequal impacts of the particles
of the dispersion medium on the valency of coagulating ion, greater will Hence, they are non-electrolyte and do
colloidal particles. be coagulating power. not precipitate the negatively charged
(a) ZnSO 4 → Zn2 + + SO 24 − emulsion.
27 Tyndall effect is more pronounced in
41 Emulsions are liquid-liquid colloidal
hydrophobic sols. (b)Na 3PO 4 → 3Na + + PO 34 − system. They can’t be broken by
28 Blood may be purified by dialysis. (c) AlCl 3 → Al 3+
+ 3Cl − adding more amount of dispersion
medium and adding emulsifying agent,
29 River water is a colloidal solution of clay
(d)K 4 [Fe(CN)6 ] → 4K+ + [Fe(CN)6 ]4 – as on adding more amount of
and sea. Water contains various
dispersion medium they become dilute
electrolytes. When river water comes in Since, in AlCl 3 , the valency of positive and on adding emulsifying agent they
contact with sea water, then the ion (coagulating ion) is highest, it is the get stabilises.
electrolytes present in sea water most powerful coagulating agent
coagulate the suspended colloidal among the given to coagulate the SESSION 2
particles which ultimately settle down at negative colloid.
the point of contact. 1 Freundlich adsorption isotherm
34 As coagulating power is inversely equation is given as
30 Fe(OH)3 is a positively charged sol, proportional to coagulation value, the x
= kp1/ n
thus coagulated by negative ion ratio of their coagulating powers will be m
(anion). Smaller the charge on anion, coagulating power of AlCl 3 On taking log both sides
smaller is its coagulating power or =
coagulating power of NaCl x 1
higher is its flocculation value. log = log k + log p
coagulating value of NaCl 52 m n
(a)KBr → K + + Br − =
coagulating valueof AlCl 3 0.093 x 1
or log = log 10 + log 0.5
(b)K 2SO 4 → 2K+ + SO 24 − m n
= 559:1
1
(c)K 2CrO 4 → 2K+ + CrO 24 − 3+ (Q slope = = tan θ = tan 45° = 1)
35 Al ions coagulate the negative mud n
(d) 4 [Fe(CN)6 ] → 4K++ [Fe(CN)6 ]4− particles. x 1
log = 1 + log (5 × 10−1 )
Q Br − has smaller charge. 36 Bleeding due to cut can be stopped by m 1
x
∴ KBr is least effective in coagulating
applying FeCl 3 solution or alum. This is log = 1 + 0.6990 − 1= 0.6990
due to coagulation of negatively m
Fe(OH)3 sol.
charged colloidal blood particles x
=antilog 0.6990
31 The process of settling of colloidal (albuminoid substance) by positively m
particles due to the neutralisation of their charged Fe 3+ ions. These substances x
charge by any means is called or = 5.00 g
are used as styptic (which check the m
coagulation. flow of blood).
2 Gold number is the number of 6 A catalyst effect both forward and 11 SnO 2 dissolves in NaOH forming
milligrams of a hydrophilic colloid that backward reactions to the same extent Na 2SnO 3
will just prevent the coagulation of 10 in a reversible reaction and thus, helps
mL of a gold sol on addition of 1 mL of in the achievement of equilibrium SnO 2 + 2NaOH → Na 2SnO 3 + H2O
10% NaCl solution. quicker. SnO 2−
3 is adsorbed by SnO 2 forming
∴Gold number = 0.25 × 1000 = 250 Thus, it does not have any effect on negatively charged colloidal sol.
spontaniety of a reaction. [SnO 2 ]SnO 32− : 2Na +
3 Volume of the gold dispersed in one litre
water 7 Extent of adsorption = kp 1/ n
(Freundlich
12 Negatively charged colloidal sol is
mass 1.9 × 10−4 g adsorprtion isotherm) formed when AgNO 3 is completely
= =
density 19 g cm−3 The amount of gas adsorbed does not precipitated as AgI and extra KI is
increase as rapidly as the pressure. adsorbed on AgI.
⇒ = 1 × 10−5 cm−3 ap
The extent of adsorption = Ag + + I− → AgI
Radius of gold sol particles = 10 nm (1+ bp)
AgI + I− → [AgI]I−
= 10 × 10−9 m = 10 × 10−7 cm (Langmuir - adsorption isotherm)
Thus, [Ag ] <[I− ]
+

⇒ = 10−6 cm where, k, a, b are constant and p is

pressure. 3[AgI]I− + Fe 3 + → 3AgI + FeI3
4 3
Volume of the gold sol particles = πr 3 mol 1mol
1
3 8 The factors which are responsible for the 1 mol mol
3
4 22 increase in the rate of surface catalysed
= × × (10−6 )3 Thus, 1 mol of [AgI] I− is coagulated by
3 7 reaction are as
the addition of 1 mol of AgNO 3 or 1/2
⇒ . × 10−18 cm3
= 419 (i) A catalyst provides proper orientation
mol Pb(NO 3 )2 or 1/3 mol of Fe(NO 3 )3 .
for the reactant molecules to react
Number of gold sol particles in 1 × 10−5 (ii) Heat of adsorption of reactants on 13 50 mL of 1 M oxalic acid
cm 3 the catalyst, helps reactant [(COOH)2 ⋅ 2H2O] = 50 millimol
1 × 10−5 molecules to overcome activation = 0.050 mol = 0.050 × 126 g = 6.3 g
= energy.
4.19 × 10−18 50 mL of 0.5 M oxalic acid = 315
. g
(iii) Adsorption increases the local
⇒ = 2.38 × 1012 concentration of reactant molecules ∴Oxalic acid adsorbed on 0.5 g charcoal
Number of gold sol particles in one mm3 on the surface of the catalyst. = 6.3 − 315
. = 315
. g
2.38 × 1012
9 The reactions which are catalysed by ∴ Amount of oxalic acid adsorbed per
= ⇒ = 2.38 × 106 .
319
106 one of the product formed are called gram of charcoal = = 6.3 g
auto-catalysis reactions and the 0.5
4 Order of activation energy is C < B < A. product is called auto-catalyst, e.g. 1
A catalyst increases the rate of reaction 14 Q Protective power ∝
by decreasing activation energy. So, 2AsH3 (g ) → 2As(g ) + 3H2 (g ) gold number
the order of ease of reaction is x 1 ∴ Order of protective power will be,
10 log = log K + log p
C > B > A. m n Gelatin > haemoglobin > sodium acetate
5 As the adsorption process is 1 (0.005) (0.05) (0.7)
From y = mx + c, slope = tan 45° = 1
exothermic, the physical adsorption n
and log K = 0.3010
15 Size of colloidal particles = 1 to 1000 nm
occurs readily at low temperature and
4 3 4
decreases with increasing temperature K =2 VC = πr = π(10)3
(in accordance to Le-chatelier’s 3 3
x Size of true solution particles ≈1nm
principle, exothermic process favours log = log 2 + 1 log 02
.
backward reaction, thus adsorption m 4
decreases with increase in Vs = π(1)3
= log 2 + log 02
. = log 0.4 3
temperature). In other words, VC
x = 103
adsorption increases with decrease in ∴ = 0.4 Thus,
m Vs
temperature.