Surface chemistry deals with phenomena that occur
at the surfaces or interfaces. The interface or surface
is represented by separating the bulk phases by a
hyphen or a slash. For example, the interface between
a solid and a gas may be represented by solid-gas
or solid/gas. Due to complete miscibility, there is no
interface between the gases. The bulk phases that
we come across in surface chemistry may be pure
compounds or solutions. The interface is normally a
few molecules thick but its area depends on the size
of the particles of bulk phases. Many important
phenomena, noticeable amongst these being
corrosion, electrode processes, heterogeneous
catalysis, dissolution and crystallisation occur at
interfaces. The subject of surface chemistry finds
many applications in industry, analytical work and
daily life situations.
To accomplish surface studies meticulously, it
becomes imperative to have a really clean surface.
Under very high vacuum of the order of 10
–8
to 10
–9
pascal, it is now possible to obtain ultra clean surface
of the metals. Solid materials with such clean
surfaces need to be stored in vacuum otherwise these
will be covered by molecules of the major components
of air namely dioxygen and dinitrogen.
In this Unit, you will be studying some important
features of surface chemistry such as adsorption,
catalysis and colloids including emulsions and gels.
Surface Chemistry
5
Surface Chemistry
After studying this Unit, you will be
able to
• describe interfacial phenomenon
and its significance;
• define adsorption and classify it
into physical and chemical
adsorption;
• explain mechanism of adsorption;
• explain the factors controlling
adsorption from gases and
solutions on solids;
• explain adsorption results on the
basis of Freundlich adsorption
isotherms;
• appreciate the role of catalysts in
industry;
• enumerate the nature of colloidal
state;
• describe preparation, properties
and purification of colloids;
• classify emulsions and describe
their preparation and properties;
• describe the phenomenon of gel
formation;
• list the uses of colloids.
Objectives
Some of the most important chemicals are produced industrially by
means of reactions that occur on the surfaces of solid catalysts.
Unit
Unit
Unit
Unit
Unit
5
2020-21
124Chemistry
There are several examples, which reveal that the surface of a solid has the
tendency to attract and retain the molecules of the phase with which it
comes into contact. These molecules remain only at the surface and do
not go deeper into the bulk. The accumulation of molecular species
at the surface rather than in the bulk of a solid or liquid is termed
adsorption. The molecular species or substance, which concentrates or
accumulates at the surface is termed adsorbate and the material on the
surface of which the adsorption takes place is called adsorbent.
Adsorption is essentially a surface phenomenon. Solids, particularly
in finely divided state, have large surface area and therefore, charcoal,
silica gel, alumina gel, clay, colloids, metals in finely divided state, etc.
act as good adsorbents.
Adsorption in action
(i) If a gas like O
2
, H
2
, CO, Cl
2
, NH
3
or SO
2
is taken in a closed vessel
containing powdered charcoal, it is observed that the pressure of the
gas in the enclosed vessel decreases. The gas molecules concentrate
at the surface of the charcoal, i.e., gases are adsorbed at the surface.
(ii) In a solution of an organic dye, say methylene blue, when animal
charcoal is added and the solution is well shaken, it is observed
that the filtrate turns colourless. The molecules of the dye, thus,
accumulate on the surface of charcoal, i.e., are adsorbed.
(iii) Aqueous solution of raw sugar, when passed over beds of animal
charcoal, becomes colourless as the colouring substances are
adsorbed by the charcoal.
(iv) The air becomes dry in the presence of silica gel because the water
molecules get adsorbed on the surface of the gel.
It is clear from the above examples that solid surfaces can hold
the gas or liquid molecules by virtue of adsorption. The process of
removing an adsorbed substance from a surface on which it is
adsorbed is called desorption.
In adsorption, the substance is concentrated only at the surface and
does not penetrate through the surface to the bulk of the adsorbent,
while in absorption, the substance is uniformly distributed throughout
the bulk of the solid. For example, when a chalk stick is dipped in ink,
the surface retains the colour of the ink due to adsorption of coloured
molecules while the solvent of the ink goes deeper into the stick due
to absorption. On breaking the chalk stick, it is found to be white from
inside. A distinction can be made between absorption and adsorption
by taking an example of water vapour. Water vapours are absorbed by
anhydrous calcium chloride but adsorbed by silica gel. In other words,
in adsorption the concentration of the adsorbate increases only at the
surface of the adsorbent, while in absorption the concentration is
uniform throughout the bulk of the solid.
Both adsorption and absorption can take place simultaneously
also. The term sorption is used to describe both the processes.
Adsorption arises due to the fact that the surface particles of the adsorbent
are not in the same environment as the particles inside the bulk. Inside
the adsorbent all the forces acting between the particles are mutually
5.1.1 Distinction
between
Adsorption
and
Absorption
5.1 Adsorption5.1 Adsorption
5.1 Adsorption5.1 Adsorption
5.1 Adsorption
5.1.2 Mechanism
of
Adsorption
2020-21
125 Surface Chemistry
balanced but on the surface the particles are not surrounded by atoms
or molecules of their kind on all sides, and hence they possess unbalanced
or residual attractive forces. These forces of the adsorbent are responsible
for attracting the adsorbate particles on its surface.The extent of
adsorption increases with the increase of surface area per unit mass of
the adsorbent at a given temperature and pressure.
Another important factor featuring adsorption is the heat of
adsorption. During adsorption, there is always a decrease in residual
forces of the surface, i.e., there is decrease in surface energy which
appears as heat. Adsorption, therefore, is invariably an exothermic
process. In other words, ∆H of adsorption is always negative. When a
gas is adsorbed, the freedom 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, ∆G = ∆H – T∆S,
∆G can be negative if ∆H has sufficiently high negative value as – T∆S
is positive. Thus, in an adsorption process, which is spontaneous, a
combination of these two factors makes ∆G negative. As the adsorption
proceeds, ∆H becomes less and less negative ultimately ∆H becomes
equal to T∆S and ∆G becomes zero. At this state equilibrium is attained.
There are mainly two types of adsorption of gases on solids.
If accumulation of gas on the surface of a solid occurs on account of
weak van der Waals’ forces, the adsorption is termed as physical
adsorption or physisorption. When the gas molecules or atoms are
held to the solid surface by chemical bonds, the adsorption is termed
chemical adsorption or chemisorption. The chemical bonds may be
covalent or ionic in nature. Chemisorption involves a high energy of
activation and is, therefore, often referred to as activated adsorption.
Sometimes these two processes occur simultaneously and it is not
easy to ascertain the type of adsorption. A physical adsorption at low
temperature may pass into chemisorption as the temperature is
increased. For example, dihydrogen is first adsorbed on nickel by van
der Waals’ forces. Molecules of hydrogen then dissociate to form hydrogen
atoms which are held on the surface by chemisorption.
Some of the important characteristics of both types of adsorption
are described below:
Characteristics of physisorption
(i) Lack of specificity: A given surface of an adsorbent does not show any
preference for a particular gas as the van der Waals’ forces are universal.
(ii) Nature of adsorbate: The amount of gas adsorbed by a solid
depends on the nature of gas. In general, easily liquefiable gases
(i.e., with higher critical temperatures) are readily adsorbed as van
der Waals’ forces are stronger near the critical temperatures. Thus,
1g of activated charcoal adsorbs more sulphur dioxide (critical
temperature 630K), than methane (critical temperature 190K) which
is still more than 4.5 mL of dihydrogen (critical temperature 33K).
5.1.3 Types of
Adsorption
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126Chemistry
(iii) Reversible nature: Physical adsorption of a gas by a solid is
generally reversible. Thus,
Solid + Gas l Gas/Solid + Heat
More of gas is adsorbed when pressure is increased as the
volume of the gas decreases (Le–Chateliers’s principle) and the
gas can be removed by decreasing pressure. Since the adsorption
process is exothermic, the physical adsorption occurs readily at
low temperature and decreases with increasing temperature
(Le-Chatelier’s principle).
(iv) Surface area of adsorbent: The extent of adsorption increases
with the increase of surface area of the adsorbent. Thus, finely
divided metals and porous substances having large surface areas
are good adsorbents.
(v) Enthalpy of adsorption: No doubt, physical adsorption is an
exothermic process but its enthalpy of adsorption is quite low (20–
40 kJ mol
-1
). This is because the attraction between gas molecules
and solid surface is only due to weak van der Waals’ forces.
Characteristics of chemisorption
(i) High specificity: Chemisorption is highly specific and it will
only occur if there is some possibility of chemical bonding
between adsorbent and adsorbate. For example, oxygen is
adsorbed on metals by virtue of oxide formation and hydrogen
is adsorbed by transition metals due to hydride formation.
(ii) Irreversibility: As chemisorption involves compound formation, it
is usually irreversible in nature. Chemisorption is also an
exothermic process but the process is very slow at low
temperatures on account of high energy of activation. Like most
chemical changes, adsorption often increases with rise of
temperature. Physisorption of a gas adsorbed at low temperature
may change into chemisorption at a high temperature. Usually
high pressure is also favourable for chemisorption.
(iii) Surface area: Like physical adsorption, chemisorption also
increases with increase of surface area of the adsorbent.
(iv) Enthalpy of adsorption: Enthalpy of chemisorption is high
(80-240 kJ mol
-1
) as it involves chemical bond formation.
1. It arises because of van der
Waals’ forces.
2. It is not specific in nature.
3. It is reversible in nature.
4. It depends on the nature of
gas. More easily liquefiable
gases are adsorbed readily.
5. Enthalpy of adsorption is low
(20-40 kJ mol
–1
)in this case.
1. It is caused by chemical bond
formation.
2. It is highly specific in nature.
3. It is irreversible.
4. It also depends on the nature
of gas. Gases which can react
with the adsorbent show
chemisorption.
5. Enthalpy of adsorption is high
(80-240 kJ mol
–1
) in this case.
Table 5.1: Comparison of Physisorption and Chemisorption
Physisorption Chemisorption
2020-21
127 Surface Chemistry
The variation in the amount of gas adsorbed by the adsorbent with
pressure at constant temperature can be expressed by means of a
curve termed as adsorption isotherm.
Freundlich adsorption isotherm: Freundlich, in 1909, gave an
empirical relationship between the quantity of gas adsorbed by unit
mass of solid adsorbent and pressure at a particular temperature. The
relationship can be expressed by the following equation:
x
m
= k.p
1/n
(n > 1) ... (5.1)
where x is the mass of the gas adsorbed on mass m of the
adsorbent at pressure P, k and n are constants which depend
on the nature of the adsorbent and the gas at a particular
temperature. The relationship is generally represented in the
form of a curve where mass of the gas adsorbed per gram of
the adsorbent is plotted against pressure (Fig. 5.1). These curves
indicate that at a fixed pressure, there is a decrease in physical
adsorption with increase in temperature. These curves always
seem to approach saturation at high pressure.
Taking logarithm of eq. (5.1)
log
x
m
= log k +
1
n
log p ... (5.2)
The validity of Freundlich isotherm can be
verified by plotting log
x
m
on y-axis (ordinate)
and log p on x-axis (abscissa). If it comes to be
a straight line, the Freundlich isotherm is valid,
otherwise not (Fig. 5.2). The slope of the
straight line gives the value of
1
n
. The intercept
on the y-axis gives the value of log k.
Freundlich isotherm explains the behaviour
of adsorption in an approximate manner. The
factor
1
n
can have values between 0 and 1
(probable range 0.1 to 0.5). Thus, equation (5.2)
holds good over a limited range of pressure.
5.1.4 Adsorption
Isotherms
Fig. 5.2: Freundlich isotherm
6. Low temperature is favourable
for adsorption. It decreases
with increase of temperature.
7. No appreciable activation
energy is needed.
8. It depends on the surface
area. It increases with an
increase of surface area.
9. It results into multimolecular
layers on adsorbent surface
under high pressure.
6. High temperature is favourable
for adsorption. It increases with
the increase of temperature.
7. High activation energy is
sometimes needed.
8. It also depends on the surface
area. It too increases with an
increase of surface area.
9. It results into unimolecular
layer.
195 K
244 K
273 K
x
m
p
Fig. 5.1: Adsorption isotherm
2020-21
128Chemistry
When
1
n
= 0,
x
m
= constant, the adsorption is independent of pressure.
When
1
n
= 1,
x
m
= k p, i.e.
x
m
∝ p, the adsorption varies directly
with pressure.
Both the conditions are supported by experimental results.
The experimental isotherms always seem to approach saturation at
high pressure. This cannot be explained by Freundlich isotherm. Thus,
it fails at high pressure.
Solids can adsorb solutes from solutions also. When a solution of
acetic acid in water is shaken with charcoal, a part of the acid is
adsorbed by the charcoal and the concentration of the acid decreases
in the solution. Similarly, the litmus solution when shaken with charcoal
becomes colourless. The precipitate of Mg(OH)
2
attains blue colour
when precipitated in presence of magneson reagent. The colour is due
to adsorption of magneson. The following observations have been made
in the case of adsorption from solution phase:
(i) The extent of adsorption decreases with an increase in temperature.
(ii) The extent of adsorption increases with an increase of surface area
of the adsorbent.
(iii) The extent of adsorption depends on the concentration of the solute
in solution.
(iv) The extent of adsorption depends on the nature of the adsorbent
and the adsorbate.
The precise mechanism of adsorption from solution is not known.
Freundlich’s equation approximately describes the behaviour of
adsorption from solution with a difference that instead of pressure,
concentration of the solution is taken into account, i.e.,
x
m
= kC
1/n
...(5.3)
(C is the equilibrium concentration, i.e., when adsorption is complete).
On taking logarithm of the above equation, we have
log
x
m
= logk +
1
n
logC ...(5.4)
Plotting log
x
m
against log C a straight line is obtained which
shows the validity of Freundlich isotherm. This can be tested
experimentally by taking solutions of different concentrations of acetic
acid. Equal volumes of solutions are added to equal amounts of
charcoal in different flasks. The final concentration is determined in
each flask after adsorption. The difference in the initial and final
concentrations give the value of x. Using the above equation, validity
of Freundlich isotherm can be established.
The phenomenon of adsorption finds a number of applications.
Important ones are listed here:
(i) Production of high vacuum: The remaining traces of air can be
adsorbed by charcoal from a vessel evacuated by a vacuum pump
to give a very high vacuum.
5.1.5 Adsorption
from
Solution
Phase
5.1.6 Applications
of
Adsorption
2020-21
129 Surface Chemistry
(ii) Gas masks: Gas mask (a device which consists of activated charcoal
or mixture of adsorbents) is usually used for breathing in coal
mines to adsorb poisonous gases.
(iii) Control of humidity: Silica and aluminium gels are used as
adsorbents for removing moisture and controlling humidity.
(iv) Removal of colouring matter from solutions: Animal charcoal
removes colours of solutions by adsorbing coloured impurities.
(v) Heterogeneous catalysis: Adsorption of reactants on the solid
surface of the catalysts increases the rate of reaction. There are
many gaseous reactions of industrial importance involving solid
catalysts. Manufacture of ammonia using iron as a catalyst,
manufacture of H
2
SO
4
by contact process and use of finely divided
nickel in the hydrogenation of oils are excellent examples of
heterogeneous catalysis.
(vi) Separation of inert gases: Due to the difference in degree of adsorption
of gases by charcoal, a mixture of noble gases can be separated by
adsorption on coconut charcoal at different temperatures.
(vii) In curing diseases: A number of drugs are used to kill germs by
getting adsorbed on them.
(viii) Froth floatation process: A low grade sulphide ore is concentrated
by separating it from silica and other earthy matter by this method
using pine oil and frothing agent (see Unit 6).
(ix) Adsorption indicators: Surfaces of certain precipitates such as
silver halides have the property of adsorbing some dyes like eosin,
fluorescein, etc. and thereby producing a characteristic colour at
the end point.
(x) Chromatographic analysis: Chromatographic analysis based on
the phenomenon of adsorption finds a number of applications in
analytical and industrial fields.
Intext QuestionsIntext Questions
Intext QuestionsIntext Questions
Intext Questions
5.1 Write any two characteristics of Chemisorption.
5.2 Why does physisorption decrease with the increase of temperature?
5.3 Why are powdered substances more effective adsorbents than their
crystalline forms?
Potassium chlorate, when heated strongly decomposes slowly giving
dioxygen. The decomposition occurs in the temperature range of
653-873K.
2KClO
3
→ 2KCl + 3O
2
However, when a little of manganese dioxide is added, the
decomposition takes place at a considerably lower temperature range,
i.e., 473-633K and also at a much accelerated rate. The added
manganese dioxide remains unchanged with respect to its mass and
composition. In a similar manner, the rates of a number of chemical
reactions can be altered by the mere presence of a foreign substance.
5.2 Catalysis5.2 Catalysis
5.2 Catalysis5.2 Catalysis
5.2 Catalysis
2020-21
130Chemistry
The systematic study of the effect of various foreign substances on the
rates of chemical reactions was first made by Berzelius, in 1835. He
suggested the term catalyst for such substances.
Substances, which accelerate the rate of a chemical reaction and
themselves remain chemically and quantitatively unchanged after the
reaction, are known as catalysts, and the phenomenon is known as
catalysis. You have already studied about catalysts and its functioning
in Section 4.5.
Promoters and poisons
Promoters are substances that enhance the activity of a catalyst while
poisons decrease the activity of a catalyst. For example, in Haber’s
process for manufacture of ammonia, molybdenum acts as a promoter
for iron which is used as a catalyst.
N
2
(g)
+ 3H
2
(g)
Fe(s)
Mo(s)
2NH
3
(g)
Catalysis can be broadly divided into two groups:
(a) Homogeneous catalysis
When the reactants products and the catalyst are in the same phase
(i.e., liquid or gas), the process is said to be homogeneous catalysis.
The following are some of the examples of homogeneous catalysis:
(i) Oxidation of sulphur dioxide into sulphur trioxide with dioxygen
in the presence of oxides of nitrogen as the catalyst in the lead
chamber process.
2SO
2
(g) + O
2
(g)
NO(g)
2SO
3
(g)
The reactants, sulphur dioxide and oxygen, and the catalyst,
nitric oxide, are all in the same phase.
(ii) Hydrolysis of methyl acetate is catalysed by H
+
ions furnished
by hydrochloric acid.
CH
3
COOCH
3
(l) + H
2
O(l)
HCI(l)
CH
3
COOH(aq) + CH
3
OH(aq)
Both the reactants and the catalyst are in the same phase.
(iii) Hydrolysis of sugar is catalysed by H
+
ions furnished by
sulphuric acid.
H SO (l)
2 4
C H O (aq) + C H O (aq)
6 12 6 6 12 6
Glucose Fructose
Solution
C H O (aq) + H O(l)
12 22 11 2
Solution
Both the reactants and the catalyst are in the same phase.
(b) Heterogeneous catalysis
The catalytic process in which the reactants and the catalyst are in
different phases is known as heterogeneous catalysis. Some of the
examples of heterogeneous catalysis are given below:
(i) Oxidation of sulphur dioxide into sulphur trioxide in the
presence of Pt.
Pt(s)
2SO (g)
3
2SO (g)
2
The reactant is in gaseous state while the catalyst is in the
solid state.
5.2.1
Homogeneous and
Heterogeneous
Catalysis
2020-21
131 Surface Chemistry
(ii) Combination between dinitrogen and dihydrogen to form
ammonia in the presence of finely divided iron in Haber’s process.
Fe(s)
2NH (g)
3
N (g) + 3H (g)
2 2
The reactants are in gaseous state while the catalyst is in the
solid state.
(iii) Oxidation of ammonia into nitric oxide in the presence of
platinum gauze in Ostwald’s process.
Pt(s)
4NO(g) + 6H O(g)
2
4NH (g) + 5O (g)
3 2
The reactants are in gaseous state while the catalyst is in the
solid state.
(iv) Hydrogenation of vegetable oils in the presence of finely divided
nickel as catalyst.
Ni(s)
Vegetable ghee(s)Vegetable oils(l) + H (g)
2
One of the reactants is in liquid state and the other in gaseous
state while the catalyst is in the solid state.
This theory explains the mechanism of heterogeneous catalysis.
The old theory, known as adsorption theory of catalysis, was
that the reactants in gaseous state or in solutions, are adsorbed
on the surface of the solid catalyst. The increase in concentration
of the reactants on the surface increases the rate of reaction. Adsorption
being an exothermic process, the heat of adsorption is utilised in
enhancing the rate of the reaction.
The catalytic action can be explained in terms of the intermediate
compound formation, the theory of which you have already studied in
Section 4.5.1
The modern adsorption theory is the combination of intermediate
compound formation theory and the old adsorption theory. The catalytic
activity is localised on the surface of the catalyst. The mechanism involves
five steps:
(i) Diffusion of reactants to the surface of the catalyst.
(ii) Adsorption of reactant molecules on the surface of the catalyst.
(iii) Occurrence of chemical reaction on the catalyst’s surface through
formation of an intermediate (Fig. 5.3).
(iv) Desorption of reaction products from the catalyst surface, and thereby,
making the surface available again for more reaction to occur.
(v) Diffusion of reaction products away from the catalyst’s surface.
The surface of the catalyst unlike the inner part of the bulk, has
free valencies which provide the seat for chemical forces of
attraction. When a gas comes in contact with such a surface, its
molecules are held up there due to loose chemical combination. If
different molecules are adsorbed side by side, they may react with
each other resulting in the formation of new molecules. Thus,
formed molecules may evaporate leaving the surface for the fresh
reactant molecules.
This theory explains why the catalyst remains unchanged in mass
and chemical composition at the end of the reaction and is effective
5.2.2 Adsorption Theory
of Heterogeneous
Catalysis
2020-21
132Chemistry
even in small quantities. It however, does not explain the action of
catalytic promoters and catalytic poisons.
Important features of solid catalysts
(a) Activity
The activity of a catalyst depends upon the strength of chemisorption
to a large extent. The reactants must get adsorbed reasonably
strongly on to the catalyst to become active. However, they must
not get adsorbed so strongly that they are immobilised and other
reactants are left with no space on the catalyst’s surface for
adsorption. It has been found that for hydrogenation reaction, the
catalytic activity increases from Group 5 to Group 11 metals with
maximum activity being shown by groups 7-9 elements of the
periodic table (Class XI, Unit 3).
Pt
2H O(l)
2
2H (g) + O (g)
2 2
(b) Selectivity
The selectivity of a catalyst is its ability to direct a reaction to yield
a particular product selectively, when under the same reaction
conditions many products are possible. Selectivity of different
catalysts for same reactants is different. For example, starting with
H
2
and CO, and using different catalysts, we get different products.
Thus, it can be inferred that the action of a catalyst is highly selective
in nature. As a result a substance which acts as a catalyst in one
reaction may fail to catalyse another reaction.
The catalytic reaction that depends upon the pore structure of the
catalyst and the size of the reactant and product molecules is called
shape-selective catalysis. Zeolites are good shape-selective catalysts
because of their honeycomb-like structures. They are microporous
+
A +B
A
B
Reacting
molecules
Catalyst surface having
free valencies
Adsorption of
reacting molecules
+
A –B
A
B
Product
Catalyst
Intermediate
Adsorption of
reacting molecules
Desorption of
product molecules
Fig. 5.3
Adsorption of
reacting
molecules,
formation of
intermediate and
desorption of
products
5.2.3 Shape-
Selective
Catalysis by
Zeolites
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133 Surface Chemistry
aluminosilicates with three dimensional network of silicates in which
some silicon atoms are replaced by aluminium atoms giving
Al–O–Si framework. The reactions taking place in zeolites depend upon
the size and shape of reactant and product molecules as well as upon
the pores and cavities of the zeolites. They are found in nature as well
as synthesised for catalytic selectivity.
Zeolites are being very widely used as catalysts in petrochemical
industries for cracking of hydrocarbons and isomerisation. An important
zeolite catalyst used in the petroleum industry is ZSM-5. It converts
alcohols directly into gasoline (petrol) by dehydrating them to give a
mixture of hydrocarbons.
Enzymes are complex nitrogenous organic compounds which are
produced by living plants and animals. They are actually protein
molecules of high molecular mass and form colloidal solutions in water.
They are very effective catalysts; catalyse numerous reactions, especially
those connected with natural processes. Numerous reactions that occur
in the bodies of animals and plants to maintain the life process are
catalysed by enzymes. The enzymes are, thus, termed as biochemical
catalysts and the phenomenon is known as biochemical catalysis.
Many enzymes have been obtained in pure crystalline state from living
cells. However, the first enzyme was synthesised in the laboratory in 1969.
The following are some of the examples of enzyme-catalysed reactions:
(i) Inversion of cane sugar: The invertase enzyme converts cane sugar
into glucose and fructose.
(ii) Conversion of glucose into ethyl alcohol: The zymase enzyme
converts glucose into ethyl alcohol and carbon dioxide.
Zymase
2C H OH(aq) + 2CO (g)
2 5 2
C H O (aq)
6 12 6
Ethyl alcohol
Glucose
(iii) Conversion of starch into maltose: The diastase enzyme converts
starch into maltose.
Diastase
nC H O (aq)
12 22 11
2(C H O ) (aq) + nH O(l)
6 10 5 n 2
Maltose
Starch
(iv) Conversion of maltose into glucose: The maltase enzyme converts
maltose into glucose.
Maltase
2C H O (aq)
6 12 6
C H O (aq) + H O(l)
12 22 11 2
GlucoseMaltose
(v) Decomposition of urea into ammonia and carbon dioxide: The
enzyme urease catalyses this decomposition.
Urease
2NH (g) + CO (g)
3 2
NH CONH (aq) + H O(l)
2 2 2
(vi) In stomach, the pepsin enzyme converts proteins into peptides
while in intestine, the pancreatic trypsin converts proteins into
amino acids by hydrolysis.
(vii) Conversion of milk into curd: It is an enzymatic reaction brought
about by lacto bacilli enzyme present in curd.
5.2.4 Enzyme
Catalysis
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134Chemistry
Characteristics of enzyme catalysis
Enzyme catalysis is unique in its efficiency and high degree of specificity.
The following characteristics are exhibited by enzyme catalysts:
(i) Most highly efficient: One molecule of an enzyme may transform
one million molecules of the reactant per minute.
(ii) Highly specific nature: Each enzyme is specific for a given reaction,
i.e., one catalyst cannot catalyse more than one reaction. For
example, the enzyme urease catalyses the hydrolysis of urea only.
It does not catalyse hydrolysis of any other amide.
(iii) Highly active under optimum temperature: The rate of an enzyme
reaction becomes maximum at a definite temperature, called the
optimum temperature. On either side of the optimum temperature,
the enzyme activity decreases. The optimum temperature range
for enzymatic activity is 298-310K. Human body temperature being
310 K is suited for enzyme-catalysed reactions.
(iv) Highly active under optimum pH: The rate of an enzyme-catalysed
reaction is maximum at a particular pH called optimum pH, which
is between pH values 5-7.
(v) Increasing activity in presence of activators and co-enzymes:
The enzymatic activity is increased in the presence of certain
substances, known as co-enzymes. It has been observed that when
a small non-protein (vitamin) is present along with an enzyme, the
catalytic activity is enhanced considerably.
Activators are generally metal ions such as Na
+
, Mn
2+
, Co
2+
, Cu
2+
,
etc. These metal ions, when weakly bonded to enzyme molecules,
increase their catalytic activity. Amylase in presence of sodium
chloride i.e., Na
+
ions are catalytically very active.
(vi) Influence of inhibitors and poisons: Like ordinary catalysts, enzymes
are also inhibited or poisoned by the presence of certain substances.
The inhibitors or poisons interact with the active functional groups
on the enzyme surface and often reduce or completely destroy the
catalytic activity of the enzymes. The use of many drugs is related
to their action as enzyme inhibitors in the body.
Mechanism of enzyme catalysis
There are a number of cavities present on the surface of colloidal particles
of enzymes. These cavities are of characteristic shape and possess active
groups such as -NH
2
, -COOH, -SH, -OH, etc. These are actually the active
Table 5.2: Some Enzymatic Reactions
Enzyme Source Enzymatic reaction
Invertase Yeast Sucrose → Glucose and fructose
Zymase Yeast Glucose → Ethyl alcohol and carbon dioxide
Diastase Malt Starch → Maltose
Maltase Yeast Maltose → Glucose
Urease Soyabean Urea → Ammonia and carbon dioxide
Pepsin Stomach Proteins → Amino acids
Table 5.2 gives the summary of some important enzymatic reactions.
2020-21
135 Surface Chemistry
centres on the surface of
enzyme particles. The
molecules of the reactant
(substrate), which have
complementary shape, fit
into these cavities just like
a key fits into a lock. On
account of the presence of
active groups, an activated
complex is formed which
then decomposes to yield
the products.
Thus, the enzyme-catalysed reactions may be considered to proceed
in two steps.
Step 1: Binding of enzyme to substrate to form an activated complex.
E + S → ES
≠
Step 2: Decomposition of the activated complex to form product.
ES
≠
→ E + P
Some of the important technical catalytic processes are listed in
Table 5.3 to give an idea about the utility of catalysts in industries.
5.2.5 Catalysts in
Industry
Process Catalyst
Finely divided iron, molybdenum as promoter;
conditions: 200 bar pressure and 723-773K temp-
erature. Now-a-days, a mixture of iron oxide,
potassium oxide and alumina is used.
Platinised asbestos;
temperature 573K.
Platinised asbestos or vanadium pentoxide (V
2
O
5
);
temperature 673-723K.
1. Haber’s process for the manufacture of
ammonia
N
2
(g) + 3H
2
(g) → 2NH
3
(g)
2. Ostwald’s process for the manufacture
of nitric acid.
4NH
3
(g) + 5O
2
(g) → 4NO(g) + 6H
2
O(g)
2NO(g) + O
2
(g) → 2NO
2
(g)
4NO
2
(g) + 2H
2
O(l) + O
2
(g) → 4HNO
3
(aq)
3. Contact process for the manufacture
of sulphuric acid.
2SO
2
(g) + O
2
(g) → 2SO
3
(g)
SO
3
(g) + H
2
SO
4
(aq) → H
2
S
2
O
7
(l)
oleum
H
2
S
2
O
7
(l) + H
2
O(l) → 2H
2
SO
4
(aq)
Table 5.3: Some Industrial Catalytic Processes
Intext QuestionsIntext Questions
Intext QuestionsIntext Questions
Intext Questions
5.4 In Haber’s process, hydrogen is obtained by reacting methane with steam in
presence of NiO as catalyst. The process is known as steam reforming. Why is
it necessary to remove CO when ammonia is obtained by Haber’s process?
5.5 Why is the ester hydrolysis slow in the beginning and becomes faster after
sometime?
5.6 What is the role of desorption in the process of catalysis.
Enzyme
(catalyst)
Substrate
(reactants)
Enzyme-Substrate
complex
Enzyme Products
E + S E – S E + P
E EE
Active site
+ +
S
P
S
P
Fig. 5.4: Mechanism of enzyme catalysed reaction
2020-21
136Chemistry
We have learnt in Unit 2 that solutions are homogeneous systems. We
also know that sand in water when stirred gives a suspension, which
slowly settles down with time. Between the two extremes of suspensions
and solutions we come across a large group of systems called colloidal
dispersions or simply colloids.
A colloid is a heterogeneous system in which one substance is
dispersed (dispersed phase) as very fine particles in another substance
called dispersion medium.
The essential difference between a solution and a colloid is that of
particle size. While in a solution, the constituent 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. Colloidal
particles are larger than simple molecules but small enough to remain
suspended. Their range of diameters is between 1 and 1000 nm
(10
–9
to 10
–6
m).
Colloidal particles have an enormous surface area per unit mass as
a result of their small size. Consider a cube with 1 cm side. It has a
total surface area of 6 cm
2
. If it were divided equally into 10
12
cubes,
the cubes would be the size of large colloidal particles and have a total
surface area of 60,000 cm
2
or 6 m
2
. This enormous surface area leads
to some special properties of colloids to be discussed later in this Unit.
Colloids are classified on the basis of the following criteria:
(i) Physical state of dispersed phase and dispersion medium
(ii) Nature of interaction between dispersed phase and dispersion
medium
(iii) Type of particles of the dispersed phase.
Depending upon whether the dispersed phase and the dispersion
medium are solids, liquids or gases, eight types of colloidal systems
are possible. A gas mixed with another gas forms a homogeneous
mixture and hence is not a colloidal system. The examples of the
various types of colloids along with their typical names are listed
in Table 5.4.
Many familiar commercial products and natural objects are colloids.
For example, whipped cream is a foam, which is a gas dispersed in a
5.3 Colloids5.3 Colloids
5.3 Colloids5.3 Colloids
5.3 Colloids
5.4.1
Classification
Based on Physical
State of Dispersed
Phase and
Dispersion
Medium
Dispersed
phase
Solid
Solid
Solid
Liquid
Liquid
Liquid
Gas
Gas
Dispersion
medium
Solid
Liquid
Gas
Solid
Liquid
Gas
Solid
Liquid
Type of
colloid
Solid sol
Sol
Aerosol
Gel
Emulsion
Aerosol
Solid sol
Foam
Examples
Some coloured glasses and gem stones
Paints, cell fluids
Smoke, dust
Cheese, jellies
Milk, hair cream, butter
Fog, mist, cloud, insecticide sprays
Pumice stone, foam rubber
Froth, whipped cream, soap lather
Table 5.4: Types of Colloidal Systems
5.4 Classification5.4 Classification
5.4 Classification5.4 Classification
5.4 Classification
of Colloidsof Colloids
of Colloidsof Colloids
of Colloids
2020-21
137 Surface Chemistry
liquid. Firefighting foams, used at emergency airplane landings are
also colloidal systems. Most biological fluids are aqueous sols (solids
dispersed in water). Within a typical cell, proteins and nucleic acids are
colloidal-sized particles dispersed in an aqueous solution of ions and
small molecules.
Out of the various types of colloids given in Table 5.4, the most
common are sols (solids in liquids), gels (liquids in solids) and
emulsions (liquids in liquids). However, in the present Unit, we shall
take up discussion of the ‘sols’ and ‘emulsions’ only. Further, it may
be mentioned that if the dispersion medium is water, the sol is called
aquasol or hydrosol and if the dispersion medium is alcohol, it is
called alcosol and so on.
Depending upon the nature of interaction between the dispersed phase
and the dispersion medium, colloidal sols are divided into two categories,
namely, lyophilic (solvent attracting) and lyophobic (solvent repelling).
If water is the dispersion medium, the terms used are hydrophilic and
hydrophobic.
(i) Lyophilic colloids: The word ‘lyophilic’ means liquid-loving. Colloidal
sols directly formed by mixing substances like gum, gelatine, starch,
rubber, etc., with a suitable liquid (the dispersion medium) are
called lyophilic sols. An important characteristic of these sols is
that if the dispersion medium is separated from the dispersed
phase (say by evaporation), the sol can be reconstituted by simply
remixing with the dispersion medium. That is why these sols are
also called reversible sols. Furthermore, these sols are quite stable
and cannot be easily coagulated as discussed later.
(ii) Lyophobic colloids: The word ‘lyophobic’ means liquid-hating.
Substances like metals, their sulphides, etc., when simply mixed
with the dispersion medium do not form the colloidal sol. Their
colloidal sols can be prepared only by special methods (as discussed
later). Such sols are called lyophobic sols. These sols are readily
precipitated (or coagulated) on the 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. Lyophobic sols need stabilising
agents for their preservation.
Depending upon the type of the particles of the dispersed phase, colloids
are classified as: multimolecular, macromolecular and associated colloids.
(i) Multimolecular colloids: On dissolution, a large number of atoms
or smaller molecules of a substance aggregate together to form
species having size in the colloidal range (1–1000 nm). The species
thus formed are called multimolecular colloids. For example, a
gold sol may contain particles of various sizes having many atoms.
Sulphur sol consists of particles containing a thousand or more of
S
8
sulphur molecules.
(ii) Macromolecular colloids: Macromolecules (Unit 15) in suitable
solvents form solutions in which the size of the macromolecules
5.4.2
Classification
Based on Nature
of Interaction
between Dispersed
Phase and
Dispersion
Medium
5.4.3
Classification
Based on Type of
Particles of the
Dispersed Phase,
Multimolecular,
Macromolecular
and Associated
Colloids
2020-21
138Chemistry
Fig. 5.5: Hydrophobic and hydrophilic parts of stearate ion
may be in the colloidal range. Such systems are called
macromolecular colloids. These colloids are quite stable and
resemble true solutions in many respects. Examples of naturally
occurring macromolecules are starch, cellulose, proteins and
enzymes; and those of man-made macromolecules are polythene,
nylon, polystyrene, synthetic rubber, etc.
(iii) Associated colloids (Micelles): There are some substances which
at low concentrations behave as normal strong electrolytes, but at
higher concentrations exhibit colloidal behaviour due to the
formation of aggregates. The aggregated particles thus formed are
called micelles. These are also known as associated colloids.
The formation of micelles takes place only above a particular
temperature called Kraft temperature (T
k
) and above a particular
concentration called critical micelle concentration (CMC). On
dilution, these colloids revert back to individual ions. Surface active
agents such as soaps and synthetic detergents belong to this class.
For soaps, the CMC is 10
–4
to 10
–3
mol L
–1
. These colloids have
both lyophobic and lyophilic parts. Micelles may contain as many
as 100 molecules or more.
Mechanism of micelle formation
Let us take the example of soap solutions. Soap is sodium or potassium
salt of a higher fatty acid and may be represented as RCOO
–
Na
+
(e.g.,
sodium stearate CH
3
(CH
2
)
16
COO
–
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 — a long
hydrocarbon chain R (also called non-polar ‘tail’) which is hydrophobic
(water repelling), and a polar group COO
–
(also called polar-ionic ‘head’),
which is hydrophilic (water loving).
The RCOO
–
ions 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 critical micelle concentration, the anions are
pulled into the bulk of the solution and aggregate to form a spherical
2020-21
139 Surface Chemistry
medium
Ice-bath
Fig. 5.8: Bredig’s Arc method
Fig. 5.7: (a) Grease on cloth (b) Stearate ions
arranging around the grease droplet and
(c) Grease droplet surrounded by
stearate ions (micelle formed)
(a)
(b)
(c)
shape with their hydrocarbon chains
pointing towards the centre of the sphere
with COO
–
part remaining outward on
the surface of the sphere. An aggregate
thus formed is known as ‘ionic
micelle’. These micelles may contain as
many as 100 such ions.
Similarly, in case of detergents, e.g.,
sodium laurylsulphate, CH
3
(CH
2
)
11
SO
4
–
Na
+
, the polar group is –SO
4
–
along
with the long hydrocarbon chain.
Hence, the mechanism of micelle
formation here also is same as that
of soaps.
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 the
fact that soap molecules form micelle around
the oil droplet in such a way that hydrophobic
part of the stearate ions is in the oil droplet and
hydrophilic part projects out of the grease
droplet like the bristles (Fig. 5.7). Since the polar
groups can interact with water, the oil droplet
surrounded by stearate ions is now pulled in
water and removed from the dirty surface. Thus
soap helps in emulsification and washing away
of oils and fats. The negatively charged sheath
around the globules prevents them from coming
together and forming aggregates.
A few important methods for the preparation of colloids are as follows:
(a) Chemical methods
Colloidal dispersions 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.
As
2
O
3
+ 3H
2
S
Double decompostion
→
As
2
S
3
(sol) + 3H
2
O
SO
2
+ 2H
2
S
Oxidation
→
3S(sol) + 2H
2
O
2 AuCl
3
+ 3 HCHO + 3H
2
O
Reduction
→
2Au(sol) + 3HCOOH + 6HCl
FeCl
3
+ 3H
2
O
Hydrolysis
→
Fe(OH)
3
(sol) + 3HCl
Stearate
ion
Water
(a)
CO
O
COO
COO
OOC
COO
COO
COO
OOC
OOC
OOC
(b)
Ionic
micelle
Fig. 5.6: (a) Arrangement of stearate ions on the surface
of water at low concentrations of soap
(b) Arrangement of stearate ions inside the bulk
of water (ionic micelle) at critical micelle
concentrations of soap
5.4.4 Preparation
of Colloids
(b) Electrical disintegration or Bredig’s Arc method
This process involves dispersion as well as
condensation. Colloidal sols of metals such as gold,
silver, platinum, etc., can be prepared by this
method. In this method, electric arc is struck
between electrodes of the metal immersed in the
dispersion medium (Fig. 5.8). The intense heat
produced vapourises the metal, which then
condenses to form particles of colloidal size.
2020-21
140Chemistry
Fig. 5.10: Electro-dialysis
Fig. 5.9: Dialysis
(c) Peptization
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. This causes the development of positive or
negative charge on precipitates, which ultimately break up into smaller
particles of the size of a colloid. You will learn about the phenomenon
of development of charge on solid particles and their dispersion in
Section 5.4.6 under the heading “Charge on collodial particles”.
Colloidal solutions when prepared, generally contain excessive amount
of electrolytes and some other soluble impurities. While the presence of
traces of electrolyte is essential for the stability of the colloidal solution,
larger quantities coagulate it. It is, therefore, necessary to reduce the
concentration of these soluble impurities to a requisite minimum. The
process used for reducing the amount of impurities to a requisite
minimum is known as purification of colloidal solution. The
purification of colloidal solution is carried out by the following mehods:
(i) Dialysis: It is a process of removing a dissolved
substance from a colloidal solution by means of
diffusion through a suitable membrane. Since
particles (ions or smaller molecules) in a true solution
can pass through animal membrane (bladder) or
parchment paper or cellophane sheet but not the
colloidal particles, the membrane can be used for
dialysis. The apparatus used for this purpose is called
dialyser. A bag of suitable membrane containing the
colloidal solution is suspended in a vessel through
which fresh water is continuously flowing (Fig. 5.9).
The molecules and ions diffuse through membrane into
the outer water and pure colloidal solution is left behind.
(ii) Electro-dialysis: Ordinarily, the process of dialysis is quite slow. It
can be made faster by applying an electric field if the dissolved substance
in the impure colloidal solution is only an electrolyte. The process is
then named electrodialysis. The colloidal solution is placed in a bag of
suitable membrane while pure water is taken outside. Electrodes are
fitted in the compartment as shown in Fig. 5.10. The ions present in the
colloidal solution migrate out to the oppositely charged electrodes.
(iii) Ultrafiltration: Ultrafiltration is the process of separating the
colloidal particles from the solvent and soluble solutes present in
the colloidal solution by specially prepared
filters, which are permeable to all
substances except the colloidal particles.
Colloidal particles can pass through
ordinary filter paper because the pores are
too large. However, the pores of filter paper
can be reduced in size by impregnating
with collodion solution to stop the flow of
colloidal particles. The usual collodion is
a 4% solution of nitro-cellulose in a
mixture of alcohol and ether. An ultra-filter
paper may be prepared by soaking the
5.4.5 Purification
of Colloidal
Solutions
2020-21
141 Surface Chemistry
Eye
Microscope
Tyndall cone
Scattered light
Light
source
Colloidal solution
Fig. 5.11: Tyndall effect
filter paper in a collodion solution, hardening by formaldehyde
and then finally drying it. Thus, by using ultra-filter paper, the
colloidal particles are separated from rest of the materials.
Ultrafiltration is a slow process. To speed up the process, pressure
or suction is applied. The colloidal particles left on the ultra-filter
paper are then stirred with fresh dispersion medium (solvent) to
get a pure colloidal solution.
Various properties exhibited by the colloidal solutions are described below:
(i) Colligative properties: Colloidal particles being bigger aggregates,
the number of particles in a colloidal solution is comparatively
small as compared to a true solution. Hence, the values of colligative
properties (osmotic pressure, lowering in vapour pressure,
depression in freezing point and elevation in boiling point) are of
small order as compared to values shown by true solutions at
same concentrations.
(ii) Tyndall effect: If a homogeneous solution placed
in dark is observed in the direction of light, it
appears clear and, if it is observed from a direction
at right angles to the direction of light beam, it
appears perfectly dark. Colloidal solutions viewed
in the same way may also appear reasonably clear
or translucent by the transmitted light but they
show a mild to strong opalescence, when viewed
at right angles to the passage of light, i.e., the
path of the beam is illuminated by a bluish light.
This effect was first observed by Faraday and later
studied in detail by Tyndall and is termed as
Tyndall effect. The bright cone of the light is
called Tyndall cone (Fig. 5.11). The Tyndall effect
is due to the fact that colloidal particles scatter light in all
directions in space. This scattering of light illuminates the
path of beam in the colloidal dispersion.
Tyndall effect can be observed during the projection
of picture in the cinema hall due to scattering of light by dust and
smoke particles present there. Tyndall effect is observed only when the
following two conditions are satisfied.
(i) The diameter of the dispersed particles is not much smaller than
the wavelength of the light used; and
(ii) The refractive indices of the dispersed phase and the dispersion
medium differ greatly in magnitude.
Tyndall effect is used to distinguish between a colloidal and true
solution. Zsigmondy, in 1903, used Tyndall effect to set up an
apparatus known as ultramicroscope. An intense beam of light is
focussed on the colloidal solution contained in a glass vessel. The
focus of the light is then observed with a microscope at right angles to
the beam. Individual colloidal particles appear as bright stars against
a dark background. Ultramicroscope does not render the actual colloidal
particles visible but only observe the light scattered by them. Thus,
ultramicroscope does not provide any information about the size and
shape of colloidal particles.
(iii) Colour: The colour of colloidal solution depends on the wavelength
of light scattered by the dispersed particles. The wavelength of light
further depends on the size and nature of the particles. The colour
5.4.6 Properties
of Colloidal
Solutions
2020-21
142Chemistry
Hydrated metallic oxides,
e.g., Al
2
O
3
.xH
2
O, CrO
3
.xH
2
O and
Fe
2
O
3
.xH
2
O, etc.
Basic dye stuffs, e.g.,
methylene blue sol.
Haemoglobin (blood)
Oxides, e.g., TiO
2
sol.
Metals, e.g., copper, silver,
gold sols.
Metallic sulphides, e.g., As
2
S
3
,
Sb
2
S
3
, CdS sols.
Acid dye stuffs, e.g., eosin,
congo red sols.
Sols of starch, gum, gelatin,
clay, charcoal, etc.
Positively charged sols Negatively charged sols
of colloidal solution also changes with the manner in which the
observer receives the light. For example, a mixture of milk and water
appears blue when viewed by the reflected light and red when viewed
by the transmitted light. Finest gold sol is red in colour; as the size
of particles increases, it appears purple, then blue and finally golden.
(iv) Brownian movement: When colloidal solutions are viewed under
a powerful ultramicroscope, the colloidal particles appear to be in
a state of continuous zig-zag motion all over the field of view. This
motion was first observed by the British botanist, Robert Brown,
and is known as Brownian movement (Fig. 5.12). This motion
is independent of the nature of the colloid but depends on
the size of the particles and viscosity of the solution. Smaller
the size and lesser the viscosity, faster is the motion.
The Brownian movement has been explained to be due
to the unbalanced bombardment of the particles by the
molecules of the dispersion medium. The Brownian movement
has a stirring effect which does not permit the particles to
settle and thus, is responsible for the stability of sols.
(v) Charge on colloidal particles: Colloidal particles always carry
an electric charge. The nature of this charge is the same on all
the particles in a given colloidal solution and may be either
positive or negative. A list of some common sols with the nature
of charge on their particles is given below:
Fig. 5.12: Brownian movement
The presence of equal and similar charges on colloidal particles is
largely responsible in providing stability to the colloidal solution,
because the repulsive forces between charged particles having same
charge prevent them from coalescing or aggregating when they come
closer to one another.
The charge on the sol particles is due to one or more reasons, viz.,
due to electron capture by sol particles during electrodispersion of
metals, due to preferential adsorption of ions from solution and/or
due to formulation of electrical double layer. Development of charge
on sol particles by preferential adsorption of ions is described below.
The sol particles acquire positive or negative charge by preferential
adsorption of positive or negative ions. When two or more ions are
present in the dispersion medium, preferential adsorption of the ion
2020-21
143 Surface Chemistry
common to the colloidal particle usually takes place. This can be
explained by taking the following examples:
(a) When highly diluted solution of silver nitrate is added to highly diluted
potassium iodide solution, the precipitated silver iodide adsorbs
iodide ions from the dispersion medium and negatively charged
colloidal sol results. However, when KI solution is added to AgNO
3
solution, positively charged sol results due to adsorption of Ag
+
ions
from dispersion medium.
AgI/I
–
AgI/Ag
+
Negatively charged Positively charged
(b) If FeCl
3
is added to the excess of hot water, a positively charged sol of
hydrated ferric oxide is formed due to adsorption of Fe
3+
ions. However,
when ferric chloride is added to NaOH solution a negatively charged
sol is obtained with adsorption of OH
-
ions.
Fe
2
O
3
.xH
2
O/Fe
3+
Fe
2
O
3
.xH
2
O/OH
–
Positively charged Negatively charged
Having acquired a positive or a negative charge by selective adsorption
on the surface of a colloidal particle as stated above, this layer attracts
counter ions from the medium forming a second layer, as shown below.
AgI/I
-
K
+
AgI/Ag
+
I
-
The combination of the two layers of opposite charges around the
colloidal particle is called Helmholtz electrical double layer. According
to modern views, the first layer of ions is firmly held and is termed fixed
layer while the second layer is mobile which is termed diffused layer.
Fig. 5.13 depicts the formation of double layer. Since separation of
charge is a seat of potential, the charges of opposite signs on the
fixed and diffused parts of the double layer results in a difference
in potential between these layers in the same manner as potential
difference is developed in a capacitor. This potential difference
between the fixed layer and the diffused layer of opposite charges
is called the electrokinetic potential or zeta potential.
If two particles of an insoluble material (precipitate) do not
have double layers they can come close enough and attractive
van der Waals forces pull them together. When particles possess
double layer as shown in Fig. 5.13, the overall effect is that
particles repel each other at large distances of separation. This
repulsion prevents their close approach. They remain dispersed
and colloid is stabilised.
The addition of more electrolytes to sol supresses the diffused
double layer and reduces the zita potential. This decreases the
electrostatic repulsion between particles to a large extent and colloid
precipitates. That is why colloid is particularly sensitive to
oppositely charged ions.
(vi) 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 an applied
electric potential is called electrophoresis. Positively charged
particles move towards the cathode while negatively charged
K
+
K
+
K
+
K
+
K
+
K
+
K
+
K
+
K
+
I
–
I
–
I
–
I
–
I
–
I
–
I
–
I
–
A
g
I
S
o
l
i
d
F
i
x
e
d
l
a
y
e
r
D
i
f
f
u
s
e
d
l
a
y
e
r
K
+
I
–
I
–
K
+
I
–
K
+
K
+
K
+
K
+
I
–
I
–
K
+
K
+
K
+
I
–
I
–
K
+
K
+
I
–
Fig. 5.13: Formation of
double layer
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144Chemistry
particles move towards the anode. This can be
demonstrated by the following experimental set-
up (Fig. 5.14).
When electrophoresis, i.e., movement of particles is
prevented by some suitable means, it is observed that
the dispersion medium begins to move in an electric
field. This phenomenon is termed electroosmosis.
(vii) Coagulation or precipitation: The stability of
the lyophobic sols is due to the presence of charge
on colloidal particles. If, somehow, the charge is
removed, the particles will come nearer to each other
to form aggregates (or coagulate) and settle down
under the force of gravity.
The process of settling of colloidal particles is
called coagulation or precipitation of the sol.
The coagulation of the lyophobic sols can be
carried out in the following ways:
(i) By electrophoresis: The colloidal particles move towards oppositely
charged electrodes, get discharged and precipitated.
(ii) By mixing two oppositely charged sols: Oppositely charged sols when
mixed in almost equal proportions, neutralise their charges and get
partially or completely precipitated. Mixing of hydrated ferric oxide
(+ve sol) and arsenious sulphide (–ve sol) bring them in the precipitated
forms. This type of coagulation is called mutual coagulation.
(iii) By boiling: When a sol is boiled, the adsorbed layer is disturbed
due to increased collisions with the molecules of dispersion
medium. This reduces the charge on the particles and ultimately
leads to settling down in the form of a precipitate.
(iv) By persistent dialysis: On prolonged dialysis, traces of the
electrolyte present in the sol are removed almost completely and
the colloids become unstable and ultimately coagulate.
(v) By addition of electrolytes: When excess of an electrolyte is added,
the colloidal particles are precipitated. The reason is that colloids
interact with ions carrying charge opposite to that present on
themselves. This causes neutralisation leading to their coagulation.
The ion responsible for neutralisation of charge on the particles is
called the coagulating ion. A negative ion causes the precipitation
of positively charged sol and vice versa.
It has been observed that, generally, the greater the valence of the
flocculating ion added, the greater is its power to cause precipitation.
This is known as Hardy-Schulze rule. In the coagulation of a negative
sol, the flocculating power is in the order: Al
3+
>Ba
2+
>Na
+
Similarly, in the coagulation of a positive sol, the flocculating power
is in the order: [Fe(CN)
6
]
4–
> PO
4
3–
> SO
4
2–
> Cl
–
The minimum concentration of an electrolyte in millimoles per litre
required to cause precipitation of a sol in two hours is called coagulating
value. The smaller the quantity needed, the higher will be the coagulating
power of an ion.
Fig. 5.14: Electrophoresis
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145 Surface Chemistry
Coagulation of lyophilic sols
There are two factors which are responsible for the stability of lyophilic
sols. These factors are the charge and solvation of the colloidal particles.
When these two factors are removed, a lyophilic sol can be coagulated.
This is done (i) by adding an electrolyte and (ii) by adding a suitable
solvent. When solvents such as alcohol and acetone are added to
hydrophilic sols, the dehydration of dispersed phase occurs. Under this
condition, a small quantity of electrolyte can bring about coagulation.
Protection of colloids
Lyophilic sols are more stable than lyophobic sols. This is due to the
fact that lyophilic colloids are extensively solvated, i.e., colloidal particles
are covered by a sheath of the liquid in which they are dispersed.
Lyophilic colloids have a unique property of protecting lyophobic
colloids. When a lyophilic sol is added to the lyophobic sol, the lyophilic
particles form a layer around lyophobic particles and thus protect the
latter from electrolytes. Lyophilic colloids used for this purpose are
called protective colloids.
These are liquid-liquid colloidal systems, i.e., the dispersion of finely
divided droplets in another liquid. If a mixture of two immiscible or
partially miscible liquids is shaken, a coarse dispersion of one liquid
in the other is obtained which is called
emulsion. Generally, one of the two liquids
is water. There are two types of emulsions.
(i) Oil dispersed in water (O/W type) and
(ii) Water dispersed in oil (W/O type).
In the first system, water acts as
dispersion medium. Examples of this type of
emulsion are milk and vanishing cream. In
milk, liquid fat is dispersed in water. In the
second system, oil acts as dispersion medium.
Common examples of this type are butter and cream.
Emulsions of oil in water are unstable and sometimes they separate
into two layers on standing. For stabilisation of an emulsion, a third
component called emulsifying agent is usually added. The emulsifying
agent forms an interfacial film between suspended particles and the
medium. The principal emulsifying agents for O/W emulsions are
proteins, gums, natural and synthetic soaps, etc., and for W/O, heavy
metal salts of fatty acids, long chain alcohols, lampblack, etc.
Emulsions can be diluted with any amount of the dispersion
medium. On the other hand, the dispersed liquid when mixed, forms
a separate layer. The droplets in emulsions are often negatively charged
and can be precipitated by electrolytes. They also show Brownian
movement and Tyndall effect. Emulsions can be broken into constituent
liquids by heating, freezing, centrifuging, etc.
Most of the substances, we come across in our daily life, are colloids. The
meals we eat, the clothes we wear, the wooden furniture we use, the
houses we live in, the newspapers we read, are largely composed of colloids.
Water in oilOil in water
Water
Oil
Fig. 5.15: Types of emulsions
5.65.6
5.65.6
5.6
ColloidsColloids
ColloidsColloids
Colloids
Around Us
Around Us
Around UsAround Us
Around Us
5.5 Emulsions5.5 Emulsions
5.5 Emulsions5.5 Emulsions
5.5 Emulsions
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146Chemistry
High voltage
electrode
(30000 volts
or more)
Gases
free
from
carbon
particles
Precipitated
ash
Smoke
Following are the interesting and noteworthy examples of colloids:
(i) Blue colour of the sky: Dust particles along with water suspended in air
scatter blue light which reaches our eyes and the sky looks blue to us.
(ii) Fog, mist and rain: When a large mass of air containing dust
particles, is cooled below its dewpoint, the moisture from the air
condenses on the surfaces of these particles forming fine droplets.
These droplets being colloidal in nature continue to float in air in
the form of mist or fog. Clouds are aerosols having small droplets
of water suspended in air. On account of condensation in the
upper atmosphere, the colloidal droplets of water grow bigger and
bigger in size, till they come down in the form of rain. Sometimes,
the rainfall occurs when two oppositely charged clouds meet.
It is possible to cause artificial rain by throwing electrified
sand or spraying a sol carrying charge opposite to the one on
clouds from an aeroplane.
(iii) Food articles: Milk, butter, halwa, ice creams, fruit juices, etc., are
all colloids in one form or the other.
(iv) Blood: It is a colloidal solution of an albuminoid substance. The
styptic action of alum and ferric chloride solution is due to
coagulation of blood forming a clot which stops further bleeding.
(v) Soils: Fertile soils are colloidal in nature in which humus acts as
a protective colloid. On account of colloidal nature, soils adsorb
moisture and nourishing materials.
(vi) Formation of delta: River water is a colloidal solution of clay. Sea
water contains a number of electrolytes. When river water meets the
sea water, the electrolytes present in sea water coagulate the colloidal
solution of clay resulting in its deposition with the formation of delta.
Applications of colloids
Colloids are widely used in the industry. Following are some examples:
(i) Electrical precipitation of smoke: Smoke is a colloidal solution of
solid particles such as carbon, arsenic compounds, dust, etc., in
air. The smoke, before it comes out from the chimney, is led through
a chamber containing plates having a charge opposite to that carried
by smoke particles. The particles on coming in contact with these
plates lose their charge and get precipitated. The particles thus
settle down on the floor of the chamber. The precipitator is called
Cottrell precipitator (Fig.5.16).
(ii) Purification of drinking water: The water obtained from
natural sources often contains suspended impurities.
Alum is added to such water to coagulate the suspended
impurities and make water fit for drinking purposes.
(iii) Medicines: Most of the medicines are colloidal in nature.
For example, argyrol is a silver sol used as an eye lotion.
Colloidal antimony is used in curing kalaazar. Colloidal
gold is used for intramuscular injection. Milk of
magnesia, an emulsion, is used for stomach disorders.
Colloidal medicines are more effective because they have
large surface area and are therefore easily assimilated.
Fig. 5.16: Cottrell smoke precipitator
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147 Surface Chemistry
(iv) Tanning: Animal hides are colloidal in nature. When a hide, which
has positively charged particles, is soaked in tannin, which contains
negatively charged colloidal particles, mutual coagulation takes
place. This results in the hardening of leather. This process is
termed as tanning. Chromium salts are also used in place of tannin.
(v) Cleansing action of soaps and detergents: This has already been
described in Section 5.4.3.
(vi) Photographic plates and films: Photographic plates or films are
prepared by coating an emulsion of the light sensitive silver bromide
in gelatin over glass plates or celluloid films.
(vii) Rubber industry: Latex is a colloidal solution of rubber particles which
are negatively charged. Rubber is obtained by coagulation of latex.
(viii) Industrial products: Paints, inks, synthetic plastics, rubber,
graphite lubricants, cement, etc., are all colloidal solutions.
SummarySummary
SummarySummary
Summary
Adsorption is the phenomenon of attracting and retaining the molecules of a
substance on the surface of a solid resulting into a higher concentration on the
surface than in the bulk. The substance adsorbed is known as adsorbate and the
substance on which adsorption takes place is called adsorbent. In physisorption,
adsorbate is held to the adsorbent by weak van der Waals forces, and in
chemisorption, adsorbate is held to the adsorbent by strong chemical bond. Almost
all solids adsorb gases. The extent of adsorption of a gas on a solid depends upon
nature of gas, nature of solid, surface area of the solid, pressure of gas and
temperature of gas. The relationship between the extent of adsorption (x/m) and
pressure of the gas at constant temperature is known as adsorption isotherm.
A catalyst is a substance which enhances the rate of a chemical reaction without
itself getting used up in the reaction. The phenomenon using catalyst is known as
catalysis. In homogeneous catalysis, the catalyst is in the same phase as are the
reactants, and in heterogeneous catalysis the catalyst is in a different phase from
that of the reactants.
Colloidal solutions are intermediate between true solutions and suspensions.
The size of the colloidal particles range from 1 to 1000 nm. A colloidal system consists
of two phases - the dispersed phase and the dispersion medium. Colloidal systems
are classified in three ways depending upon (i) physical states of the dispersed phase
and dispersion medium (ii) nature of interaction between the dispersed phase and
dispersion medium and (iii) nature of particles of dispersed phase. The colloidal
systems show interesting optical, mechanical and electrical properties. The process
of changing the colloidal particles in a sol into the insoluble precipitate by addition
of some suitable electrolytes is known as coagulation. Emulsions are colloidal systems
in which both dispersed phase and dispersion medium are liquids. These can be of:
(i) oil in water type and (ii) water in oil type. The process of making emulsion is
known as emulsification. To stabilise an emulsion, an emulsifying agent or emulsifier
is added. Soaps and detergents are most frequently used as emulsifiers. Colloids find
several applications in industry as well as in daily life.
Intext QuestionsIntext Questions
Intext QuestionsIntext Questions
Intext Questions
5.7 What modification can you suggest in the Hardy Schulze law?
5.8 Why is it essential to wash the precipitate with water before estimating it
quantitatively?
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148Chemistry
5.1 Distinguish between the meaning of the terms adsorption and absorption.
Give one example of each.
5.2 What is the difference between physisorption and chemisorption?
5.3 Give reason why a finely divided substance is more effective as an adsorbent.
5.4 What are the factors which influence the adsorption of a gas on a solid?
5.5 What is an adsorption isotherm? Describe Freundlich adsorption isotherm.
5.6 What do you understand by activation of adsorbent? How is it achieved?
5.7 What role does adsorption play in heterogeneous catalysis?
5.8 Why is adsorption always exothermic ?
5.9 How are the colloidal solutions classified on the basis of physical states of
the dispersed phase and dispersion medium?
5.10 Discuss the effect of pressure and temperature on the adsorption of gases
on solids.
5.11 What are lyophilic and lyophobic sols? Give one example of each type. Why
are hydrophobic sols easily coagulated ?
5.12 What is the difference between multimolecular and macromolecular colloids?
Give one example of each. How are associated colloids different from these
two types of colloids?
5.13 What are enzymes ? Write in brief the mechanism of enzyme catalysis.
5.14 How are colloids classified on the basis of
(i) physical states of components
(ii) nature of dispersed phase and
(iii) interaction between dispersed phase and dispersion medium?
5.15 Explain what is observed
(i) when a beam of light is passed through a colloidal sol.
(ii) an electrolyte, NaCl is added to hydrated ferric oxide sol.
(iii) electric current is passed through a colloidal sol?
5.16 What are emulsions? What are their different types? Give example of each type.
5.17 How do emulsifires stabilise emulsion? Name two emulsifiers.
5.18 Action of soap is due to emulsification and micelle formation. Comment.
5.19 Give four examples of heterogeneous catalysis.
5.20 What do you mean by activity and selectivity of catalysts?
5.21 Describe some features of catalysis by zeolites.
5.22 What is shape selective catalysis?
5.23 Explain the following terms:
(i) Electrophoresis (ii) Coagulation (iii) Dialysis (iv) Tyndall effect.
5.24 Give four uses of emulsions.
5.25 What are micelles? Give an example of a micellers system.
5.26 Explain the terms with suitable examples:
(i) Alcosol (ii) Aerosol (iii) Hydrosol.
5.27 Comment on the statement that “colloid is not a substance but a state of
substance”.
ExercisesExercises
ExercisesExercises
Exercises
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