S Surface Chemistry 573

Chapter

14
Surface Chemistry

“The branch of physical chemistry, which deals the Interface : Any surface is a Adsorbate and Adsorbent :
nature of surfaces and also with the chemical and plane which separates any The substance which gets
physical processes which takes place on the surfaces, is two phases in contact with adsorbed on any surface is
called surface chemistry”. each other. The plane which called adsorbate for
separates any two phase is example, if a gas gets
In surface chemistry, we study the phenomenon of generally called an adsorbed on to the surface
adsorption, catalysis and colloidal properties. interface between the two of a solid, then the gas is
Adsorption phases. termed as the adsorbate.
(1) Definition : The phenomenon of attracting The substance on the
surface of which adsorption
and retaining the molecules of a substance on the
takes place is called
surface of a liquid or solid resulting in to higher
adsorbent.
concentration of the molecules on the surface is called
adsorption.
Desorption : The removal Absorption : When the
(2) Causes of adsorption : Unbalanced forces of of the adsorbed substance molecules of a substance are
attraction or free valencies which is present at the from a surface is called uniformly distributed
solid or liquid surface, have the property to attract and desorption. throughout the body of a
retain the molecules of a gas or a dissolved substance solid or liquid. This
on to their surfaces with which they come in contact. phenomenon is called
Example : Ammonia gas placed in contact with absorption.

charcoal gets adsorbed on the charcoal whereas Sorption : The phenomenon Occlusion : When
in which adsorption and adsorption of gases occur on
ammonia gas placed in contact with water gets
absorption occur the surface of metals this is
absorbed into water,
simultaneously is called called occlusion.
Table : 14.1 Some basic terms used in adsorption sorption.
Mc. Bain introduced a
general term sorption
describeing both the
processes, however
adsorption is instantaneous
i.e. a fast process while
absorption is a slow process.

(3) Difference between adsorption and absorption

Adsorption Absorption
It is a surface phenomenon. It concerns with the whole
mass of the absorbent.
 574 Surface Chemistry
In it, the substance is only It implies that a substance is (v) For a process to be spontaneous, the
retained on the surface and uniformly distributed, thermodynamic requirement is that G must be
does not go into the bulk or through the body of the negative, i.e. there is decrease in free energy. On the
interior of the solid or solid or liquid. basis of Gibb’s Helmholtz equation, G  H  TS , G
liquid.
can be negative if H has sufficiently high negative
In it the concentration of the In it the concentration is
value and TS has positive value.
adsorbed molecules is low.
always greater at the free Classification of adsorption
phase.
It is rapid in the beginning It occurs at the uniform Adsorption can be classified into two categories
and slows down near the rate. as described below,
equilibrium.
(1) Depending upon the concentration : In
Examples : (i) Water Examples : (i) Water
adsorption the concentration of one substance is
vapours adsorbed by silica vapours absorbed by
gel. anhydrous CaCl2
different at the surface of the other substance as
(ii) NH3 is adsorbed by (ii) NH3 is absorbed in water compared to adjoining bulk or interior phase.
charcoal. forming NH4OH (i) Positive adsorption : If the concentration of
adsorbate is more on the surface as compared to its
(4) Surface forces : Only the surface atoms of an concentration in the bulk phase then it is called
adsorbent play an active role in adsorption. These positive adsorption.
atoms posses unbalanced forces of various types such Example : When a concentrated solution of KCl is
as, Vander Waal’s forces and chemical bond forces. shaken with blood charcoal, it shows positive
Thus, the residual force-field on a free surface adsorption.
which is responsible for adsorption is produced. For (ii) Negative adsorption : If the concentration of
example, when a solid substance is broken into two the adsorbate is less than its concentration in the bulk
pieces, two new surfaces are formed and therefore, the then it is called negative adsorption.
number of unbalanced forces becomes more. As a result
the tendency for adsorption become large. Example : When a dilute solution of KCl is shaken
with blood charcoal, it shows negative adsorption.
(5) Reversible and Irreversible adsorption : The
adsorption is reversible, if the adsorbate can be easily (2) Depending upon the nature of force existing
removed from the surface of the adsorbent by physical between adsorbate molecule and adsorbent
methods.If the adsorbate can not be easily removed (i) Physical adsorption : If the forces of
from the surface of the adsorbent is called irreversible attraction existing between adsorbate and adsorbent
adsorption. are Vander Waal’s forces, the adsorption is called
Example for reversible adsorption: A gas adsorbed physical adsorption. This type of adsorption is also
on a solid surface can be completely removed in vacuum. known as physisorption or Vander Waal’s adsorption.
It can be easily reversed by heating or decreasing the
Example for irreversible adsorption: Adsorption of
pressure.
O2 on tungusten adsorbent.
(ii) Chemical adsorption : If the forces of
(6) Characteristics of adsorption
attraction existing between adsorbate particles and
(i) Adsorption refers to the existence of a higher adsorbent are almost of the same strength as chemical
concentration of any particular component at the bonds, the adsorption is called chemical adsorption.
surface of a liquid or a solid phase. This type of adsorption is also called as chemisorption
(ii) Adsorption is accompanied by decrease in the or Langmuir adsorption. This type of adsorption
G (free energy change) of the system when G  0 , cannot be easily reversed.
adsorption equilibrium is said to be established. Comparison between physisorption and
chemisorption
(iii) Adsorption is invariably accompanied by
evolution of heat, i.e. it is an exothermic process. In Physisorption Chemisorption
other words, H of adsorption is always negative. (Vander Waal's adsorption) (Langmuir adsorption)
Low heat of adsorption High heat of adsorption in
usually in range of 20-40 the range of 50-400 kJ/mol
(iv) When a gas is adsorbed, the freedom of kJ/mol
movement of its molecules becomes restricted. On Force of attraction are Forces of attraction are
account of it decrease in the entropy of the gas after Vander Waal's forces. chemical bond forces.
adsorption, i.e. S is negative. It is reversible It is irreversible
S Surface Chemistry 575
It is usually takes place at It takes place at high magnitude of adsorption should decrease with rise in
low temperature and temperature. temperature.
decreases with increasing
temperature.
P - Constant P-
It is related to the case of It is not related.
Constant
liquefication of the gas.
It forms multimolecular It forms monomolecular x/m x/m
layers. layers.
It does not require any It requires high activation
activation energy. energy. Temperatur Temperatur
e
Physical e
Chemical
High pressure is favourable. High pressure is favourable.
Decrease of pressure causes Decrease of pressure does adsorption adsorption
desorption not cause desorption. (ii) The relationship between the extent of
It is not very specific. It is highly specific. adsorption and temperature at any constant pressure is
called adsorption isobar.
Factors which affect the extent of adsorption :
The following are the factors which affect the (iii) A physical adsorption isobar shows a
adsorption, decrease in x/m (where ‘m’ is the mass of the adsorbent
and ‘x’ that of adsorbate) as the temperature rises.
(1) Nature of the adsorbate (gas) and adsorbent
(iv) The isobar of chemisorption show an increase
(solid)
in the beginning and then decrease as the temperature
(i) In general, easily liquefiable gases e.g., CO2,
rises.
NH3, Cl2 and SO2 etc. are adsorbed to a greater extent
than the elemental gases e.g. H2, O2, N2, He etc. (while Adsorption isotherms
chemisorption is specific in nature.) A mathematical equation, which describes the
(ii) Porous and finely powdered solid e.g. relationship between pressure (p) of the gaseous
charcoal, fullers earth, adsorb more as compared to the adsorbate and the extent of adsorption at any fixed
hard non-porous materials. Due to this property temperature, is called adsorption isotherms.
powdered charcoal is used in gas masks. The extent of adsorption is expressed as mass of
(2) Surface area of the solid adsorbent the adsorbate adsorbed on one unit mass of the
(i) The extent of adsorption depends directly upon adsorbent.
the surface area of the adsorbent, i.e. larger the surface Thus, if x g of an adsorbate is adsorbed on m g of
area of the adsorbent, greater is the extent of the adsorbent, then
adsorption. x
Extent of adsorption 
(ii) Surface area of a powdered solid adsorbent m
depends upon its particle size. Smaller the particle size, Various adsorption isotherms are commonly
greater is its surface area. employed in describing the adsorption data.
(3) Effect of pressure on the adsorbate gas (1) Freundlich adsorption isotherm
(i) An increase in the pressure of the adsorbate (i) Freundlich adsorption isotherm is obeyed by
gas increases the extent of Adsorption tends to the adsorptions where the adsorbate forms a
adsorption. reach limiting value monomolecular layer on the surface of the adsorbent.
adsorption

(ii) At low
Extent of

1
x
temperature, the extent of  kp n (Freundlich adsorption isotherm) or
m
adsorption increases
Adsorption increases x 1
rapidly with pressure. rapidly at the beginning
log  log k  log p
m n
(iii) Small range of Pressure
where x is the weight of the gas adsorbed by m
pressure, the extent of
gm of the adsorbent at a pressure p, thus x/m
adsorption is found to be directly proportional to the
represents the amount of gas adsorbed by the
pressure.
adsorbents per gm (unit mass), k and n are constant at
(iv) At high pressure (closer to the saturation a particular temperature and for a particular adsorbent
vapour pressure of the gas), the adsorption tends to and adsorbate (gas), n is always greater than one,
achieve a limiting value. indicating that the amount of the gas adsorbed does
(4) Effect of temperature not increase as rapidly as the pressure.
(i) As adsorption is accompanied by evolution of (ii) At low pressure, the extent of adsorption
x
heat, so according to the Le-Chatelier’s principle, the varies linearly with pressure.  p'
m
 576 Surface Chemistry
(iii) At high pressure, it becomes independent of temperature. Their values can be determined from the
x experimental data.
pressure.  p0
m Limitation of Langmuir theory
x
(iv) At moderate pressure depends upon (a) Langmuir’s theory of unimolecular adsorption
m
1 is valid only at low pressures and high temperatures.
x
pressure raised to powers  pn (b) When the pressure is increased or
m
x x temperature is lowered, additional layers are formed.
 p1  p0
m m This has led to the modern concept of multilayer
adsorption.
1
(x/m)

slope  Adsorption from solutions

log

x/m n
x
 p1 / n intercept = log (1) The process of adsorption can take place from
m
x/m k solutions also.
p log p
(2) In any solution, there are two (or more)
Freundlich adsorption Plot of log x/m against log p for components ; solute and solvent. The solute may be
isotherm: plot of x/m the adsorption of a gas on a solid present in the molecular or ionic form.
against p
(3) The extent of adsorption from solution
(2) The Langmuir - adsorption isotherms depends upon the concentration of the solute in the
(i) One of the drawbacks of Freundlich adsorption solution, and can be expressed by the Freundlich
isotherm is that it fails at high pressure of the gas. isotherm.
Irving Langmuir in 1916 derived a simple adsorption (4) The Freundlich adsorption isotherm for the
isotherm, on theoretical considerations based on x
1

kinetic theory of gases. This is named as Langmuir adsorption from solution is,  kc n where, x is the
m
adsorption isotherm. mass of the solute adsorbed, m is the mass of the solid
(a) Adsorption takes place on the surface of the adsorbent, c is the equilibrium concentration of the
solid only till the whole of the surface is completely solute in the solution, n is a constant having value
covered with a unimolecular layer of the adsorbed gas. greater than one,
k is the proportionality constant, (The value of k
(b) Adsorption consists of two opposing
depends upon the nature of solid, its particle size,
processes, namely Condensation of the gas molecules
temperature, and the nature of solute and solvent etc.)
on the solid surface and Evaporation (desorption) of
(5) The plot of x/m against c is similar to that
the gas molecules from the surface back into the
gaseous phase. Freundlich adsorption isotherm. The above equations
may be written in the following form,
(c) The rate of condensation depends upon the x 1
uncovered (bare) surface of the adsorbent available for log  log k  log c where c, is the equilibrium
m n
condensation. Naturally, at start when whole of the concentration of the solute in the solution.
surface is uncovered the rate of condensation is very
high and as the surface is covered more and more, the
Application of adsorption
rate of condensation progressively decreases. On the The phenomenon of adsorption finds a number of
contrary, the rate of evaporation depends upon the applications. Important applications are given as
covered surface and hence increases as more and more follows.
of the surface is covered ultimately an equilibrium will (1) Production of high vacuum
be set up at a stage when the rate of condensation
(2) In Gas masks : This apparatus is used to
becomes equal to the rate of evaporation (adsorption adsorb poisonous gases (e.g. Cl 2 , CO, oxide of sulphur
equilibrium).
etc.) and thus purify the air for breathing.
(d) The rate of condensation also depends upon (3) For desiccation or dehumidification : These
the pressure of the gas since according the kinetic substances can be used to reduce/remove water
theory of gases, the number of molecules striking per vapours or moisture present in the air. Silica gel and
unit area is proportional to the pressure. alumina are used for dehumidification in electronic
x ap equipment.
Mathematically,  , where a and b are
m 1  bp (4) Removel of colouring matter from solution :
constants and their value depends upon the nature of (i) Animal charcoal removes colours of solutions by
gas (adsorbate), nature of the solid adsorbent and the
S Surface Chemistry 577
adsorbing coloured impurities. (ii) Animal charcoal is The phenomenon of adsorption has given an
used as decolouriser in the manufacture of cane sugar. excellent technique of analysis known as
(5) Heterogeneous catalysis : Mostly chromatographic analysis.
heterogeneous catalytic reactions proceed through the (14) In dyeing : Many dyes get adsorbed on the
adsorption of gaseous reactants on solid catalyst. For cloth either directly or by the use of mordants.
example, Catalysis
(i) Finely powdered nickel is used for the
“Catalyst is a substance which speeds up and
hydrogenation of oils.
speeds down a chemical reaction without itself being
(ii) Finely divided vanadium pentaoxide (V2 O5 ) is
used up.”
used in the contact process for the manufacture of Berzelius (1836) introduced the term catalysis and
sulphuric acid. catalyst.
(6) Separation of inert gases : Due to the Ostwald (1895) redefined a catalyst as, “A
difference in degree of adsorption of gases by charcoal, substance which changes the reaction rate without
a mixture of inert gases can be separated by adsorption affecting the overall energetics of the reaction is termed
on coconut charcoal at different low temperatures. as a catalyst and the phenomenon is known as
(7) Softening of hard water catalysis.”
(i) The hard water is made to pass through a Types of catalysis
column packed with zeolite (sodium aluminium
Catalytic reactions can be broadly divided into the
silicate) following types,
(ii) Ca++, Mg++ ions which are responsible for (1) Homogeneous catalysis : When the reactants
hardness, get adsorbed on zeolite, exchanging sodium and the catalyst are in the same phase (i.e. solid, liquid
ions. or gas). The catalysis is said to be homogeneous. The
Na 2 Al 2 Si 2 O8  CaCl 2  CaAl 2 Si 2 O8  2 NaCl following are some of the examples of homogeneous
catalysis.
(iii) The exhausted zeolite is regenerated with
(i) In the lead chamber process
10% of sodium chloride solution.
2 SO 2 (g)  O 2 (g)    2 SO 3 (g)
NO ( g )
CaAl 2 Si 2 O8  2 NaCl  Na 2 Al 2 Si 2 O8  CaCl 2
(ii) In the hydrolysis of ester
(8) De-ionisation of water
CH 3 COOCH 3 (l)  H 2 O(l)  
HCl (l)
(i) Water can be de-ionised by removing all
dissolved salts with the help of cation and anion-
exchanger resin. CH 3 COOH (l)  CH 3 OH(l)
(ii) Cation-exchanger is an organic synthetic resin (iii) In the hydrolysis of sugar
such as polystyrene-containing a macroanion C12 H 22 O11 (l) H 2 O(l)   
H 2 SO 4 (l)

(R  SO 3 etc .) which has adsorbed H+ ions.

(Sucrose solution)

(iii) A resin containing a basic group (R 3 N  etc.) C6 H 12 O6 (l)  C 6 H 12 O6 (l)

(Glucose solution) (Fructose solution)

which has adsorbed OH ions acts as anion exchanger.
(2) Heterogeneous catalysis : The catalytic
(9) In curing diseases : A number of drugs are
process in which the reactants and the catalyst are in
adsorbed on the germs and kill them or these are
different phases is known as heterogeneous catalysis.
adsorbed on the tissues and heat them.
Some of the examples of heterogeneous catalysis are
(10) Cleaning agents : Soap and detergents get
given below.
adsorbed on the interface and thus reduce the surface
tension between dirt and cloth, subsequently the dirt is (i) In contact process for H 2SO 4
removed from the cloth. 2 SO 2 (g)  O2 (g)   2 SO 3 (g)
Pt(s )
BrV2 O5
(11) Froth floatation process
A low grade sulphide ore is concentrated by (ii) In Haber’s process for NH 3
separating it from silica and other earthy matter by
this method. N 2 (g)  3 H 2 (g)   2 NH 3 (g)
Fe ( s )

(12) In adsorption indicators (iii) In Ostwald’s process for HNO 3

Surface of certain precipitates such as silver
halide, have the property of adsorbing some dyes like 4 NH 3 (g)  5 O2 (g)   4 NO (g)  6 H 2 O(g)
Pt( s )

eosin, fluorescein etc. (3) Positive catalysis : When the rate of the
(13) Chromatographic analysis reaction is accelerated by the foreign substance, it is
said to be a positive catalyst and phenomenon as
 578 Surface Chemistry
positive catalysis. Some examples of positive catalysis (i) Sodium arsenite solution is not oxidised by air.
are given below. If, however, air is passed through a mixture of the
(i) Decomposition of KClO 3 solution of sodium arsenite and sodium sulphite, both
of them undergo simultaneous oxidation. The oxidation
2 KClO 3 (s)   2 KCl (s)  3 O2 (g)
MnO 2 ( s )
of sodium sulphite, thus, induces the oxidation of
270 o C
sodium arsenite.
(ii) Oxidation of SO 2 (ii) The reduction of mercuric chloride
2 SO 2 (g)  O2 (g)  2 SO 3 (g)
V2 O 5 ( s ) (HgCl 2 ) with oxalic acid is very slow, but potassium
or Pt( s )
permanganate is reduced readily with oxalic acid. If,
(iii) Decon’s process however, oxalic acid is added to a mixture of potassium
permanganate and HgCl2 both are reduced
4 HCl (g)  O2 (g)   2Cl 2 (g)  2 H 2 O(g)
CuCl 2 ( s )
450 o C simultaneously. The reduction of potassium
(4) Negative catalysis : There are certain, permanganate, thus, induces the reduction of mercuric
substance which, when added to the reaction mixture, chloride.
retard the reaction rate instead of increasing it. These (7) Acid-base catalysis : According to the
are called negative catalyst or inhibitors and the Arrhenius and Ostwald H+ or H– ion act as a catalyst.
phenomenon is known as negative catalysis. Some (i) For example, Hydrolysis of an ester,
examples are as follows. 
CH 3 COOC 2 H 5 (l)  H 2O(l)  
 CH 3 COOH (l)  C2 H 5 OH (l)
H or
(i) Oxidation of sodium sulphite OH 

2 Na 2 SO 3 (s)  O2 (g)    2 Na 2 SO 4 (s)

Alcohol (l) (ii) Inversion of cane sugar,

(ii) Oxidation of benzaldehyde C12 H 22 O11 (l)  H 2 O 
H
 C6 H12 O6 (l) C6 H12 O6 (l)
Sugar Fructose Glucose
2C6 H 5 CHO (l)  O2 (g)   2C6 H 5 COOH (l)
Diphenyl
amine (l) (iii) Conversion of acetone into diacetone alcohol,

(iii) Tetra ethyl lead (TEL) is added to petrol to CH 3 COCH 3 (l)  CH 3 COCH 3 (l) 
OH

retard the ignition of petrol vapours on compression in
an internal combustion engine and thus minimise the
CH 3COCH 2 .C(CH 3 )2 OH(l)
knocking effect.
(5) Auto-catalysis : In certain reactions, one of
Characteristics of catalysis
the product acts as a catalyst. In the initial stages the The following are the characteristics which are
reaction is slow but as soon as the products come into common to must of catalytic reactions.
existences the reaction rate increases. This type of (1) A catalyst remains unchanged in mass and
phenomenon is known as auto-catalysis. Some chemical composition at the end of the reaction.
examples are as follows, (2) A small quantity of the catalyst is generally
(i) The rate of oxidation of oxalic acid by acidified sufficient to catalyses almost unlimited reactions
potassium permanganate increases as the reaction (i) For example, in the decomposition of hydrogen
progresses. This acceleration is due to the presence of peroxide, one gram of colloidal platinum can catalyses
Mn 2  ions which are formed during reaction. Thus 10 8 litres of hydrogen peroxide.
Mn 2  ions act as auto-catalyst. (ii) In Friedel craft’s reaction, anhydrous
5 H2C2O4  2KMnO 4  3 H2SO 4  2 MnSO 4  K2SO 4 aluminium chloride is required in relatively large
amount to the extent of 30% of the mass of benzene,

10 CO2  8 H 2O C6 H6  C2 H5 Cl   C6 H5 C2 H5  HCl

AlCl 3

(ii) When nitric acid is poured on copper, the (3) The catalyst can not initiate the reaction:
reaction is very slow in the beginning, gradually the The function of the catalyst is to alter the speed of the
reaction becomes faster due to the formation of nitrous reaction rather than to start it.
acid during the reaction which acts as an auto-catalyst. (4) The catalyst is generally specific in nature:
(6) Induced catalysis : When one reaction A substance, which acts as a catalyst for a particular
influences the rate of other reaction, which does not reaction , fails to catalyse the other reaction , different
occur under ordinary conditions, the phenomenon is catalysts for the same reactant may for different
known as induced catalysis. Some examples are as products.
follows, Examples :
Al 2O3 C 2 H 4 (g)  H 2 O(g)
(Dehy dration)

C 2 H 5 OH (l)
Cu
CH 3 CHO (g)  H 2 (g)
Cu (Dehy drogenation )

Cu
CO 2 (g)  H 2 (g)
(Dehy drogenation)
S Surface Chemistry 579
(i) According to the collision theory, a reaction
occurs on account of effective collisions between the
reacting molecules.
(ii) For effective collision, it is necessary that the
molecules must possess a minimum amount of energy
known as activation energy (Ea).
(iii) After the collision molecules form an
activated complex which dissociate to yield the product
molecules.
(iv) The catalyst provides a new pathway
(5) The catalyst can not change the position of involving lower amount of activation energy. Thus,
equilibrium : The catalyst catalyse both forward and
Ea Ea Ea
backward reactions to the same extent in a reversible
 RT
 – RT 
reaction and thus have no effect on the equilibrium Decreases
Decreases –
Increases
constant.
(6) Catalytic promoters : Substances which
themselves are not catalysts, but when mixed in small e–Ea/RT k
quantities with the catalysts increase their efficiency  Increases  Reaction speeds
Increases up
are called as promoters or activators.
(i) For example, in Haber’s process for the
synthesis of ammonia, traces of molybdenum increases larger number of effective collisions occur in
the activity of finely divided iron which acts as a the presence of a catalyst in comparison to
catalyst. effective collisions at the same temperature in
absence of a catalyst. Hence the presence of a
(ii) In the manufacture of methyl alcohol from
catalyst makes the reaction to go faster.
water gas (CO  H 2 ) , chromic oxide (Cr2 O3 ) is used as a
(v) Figure shows that activation energy E a ,
promoter with the catalyst zinc oxide (ZnO ) .
in absence of a catalyst is higher than the
(7) Catalytic poisons : Substances which destroy activation energy Ea, in presence of a catalyst.
the activity of the catalyst by their presence are known
(vi) ER and Ep represent the average
as catalytic poisons.
energies of reactants and products. The difference
(i) For example, the presence of traces of
gives the value of G , i.e., G  ER  EP
arsenious oxide ( As 2O3 ) in the reacting gases reduces
Uncatalysed
the activity of platinized asbestos which is used as complex
catalyst in contact process for the manufacture of
Energy
sulphuric acid.
Chemical potential

barrier
(ii) The activity of iron catalyst is destroyed by Catalysed
energy

the presence of H 2 S or CO in the synthesis of complex

Ea
ammonia by Haber’s process.
(iii) The platinum catalyst used in the oxidation of Ea
hydrogen is poisoned by CO .
ER
(8) Change of temperature alters the rate of Reactants
Initial G° of
catalytic reaction as it does for the same reaction in (A+B) reaction
state
absence of catalyst : By increasing the temperature, EP
there is an increase in the catalytic power of a catalyst Final state Products (C +
but after a certain temperature its power begins to Reaction D)

decrease. A catalyst has thus, a particular temperature sequence

at which its catalytic activity is maximum. This
Theories of catalysis
temperature is termed as optimum temperature.
(9) A positive catalyst lowers the activation There are two theories of catalysis which is
energy described as follows.
(1) Intermediate compound theory
 580 Surface Chemistry
(i) This theory was proposed by Clement and thus, termed as bio-chemical catalysts and the
Desormes in 1806. According to this theory, the desired phenomenon is known as bio-chemical catalysis.
reaction is brought about by a path involving the (4) Nitrogenase an enzyme present in bacteria on
formation of an unstable intermediate compound, the root nodules of leguminous plants such as peas and
followed by its decomposition into the desired end beans, catalyses the conversion of atmospheric N 2 to
products with the regeneration of the catalyst.
NH 3 .
(ii) The intermediate compund may be formed in
(5) In the human body, the enzyme carbonic
either of two ways
anhydrase catalyses the reaction of CO 2 with H 2 O ,
(a) When the intermediate compound is reactive
and reacts with the other reactants. CO2 (aq)  H 2O(l)  H  (aq.)  HCO 3 (aq.)
AB  X  BX  A The forward reaction occurs when the blood takes
intermedia te
up CO 2 in the tissues, and the reverse reaction occurs
BX  C  CB  X .....(i) when the blood releases CO 2 in lungs.
(b) When the intermediate is unstable and
(6) In manufacturing of ethyl alcohol
decomposes to give the final product.
(i)
A  B  X  ABX  AB  X .....(ii)
intermedia te C12 H 22 O11 (l)  H 2 O(l)   C6 H12 O6 (l) C6 H12 O6 (l)
Invertase

Glucose Fructose
Where, A, B and C are the reactant molecules and
X is the molecule of the catalyst. The first type of C6 H12 O6 (l)  2C 2 H 5 OH (l)  2CO 2 (l)
Zy mase

reaction sums up to, AB  C  CB  A

(ii) Starch (l)   Maltose (l)
Diastase

While the second to, A  B  AB in many cases,

the intermediate compounds postulated to be formed Maltose    Glucose 
Maltase
 Alcohol
Zyamase

are known compounds and often their presence is Activity and Selectivity
detected.
(1) Activity : Activity is the ability of catalysts to
(2) Adsorption theory
accelerate chemical reaction, the degree of acceleration
(i) This theory is applicable to reactions between can be as high as 10 10 times in certain reactions. For
gases in the presence of a solid catalyst. Some typical example reaction between H 2 and O 2 to form H 2 O in
examples are as follows.
presence of platinum as catalyst takes place with
(ii) The contact process for the oxidation of SO 2
explosive violence.
to SO 3 with atmospheric oxygen in the presence of In absence of catalyst, H 2 and O 2 can be stored
platinum as the catalyst. indefinitely without any reaction.
(iii) The Haber’s process for the synthesis of (2) Selectivity : Is the ability of catalysts to direct
ammonia with iron as the catalyst. reaction to yield particular products (excluding other).
(iv) Adsorption results in the loosening of the Example :
chemical bonds in the reactant molecules, so that their CH 3
rupture becomes easier. This is confirmed by the
(i) n  heptane 
Pt

observed lower activation energies for heterogeneous
catalytic reactions in the presence of the catalysts as Toluen
compared to that for the same reaction in the absence O
e ||
(ii) CH 3 CH  CH 2   CH 2  CHCH
BiMoO 4
of the catalyst.
Acrolein
Enzyme catalysis
Zeolite (Shape selective catalysis)
(1) Enzymes are complex nitrogenous substances
(1) Zeolite are alumino–silicates of the general
these are actually protein molecules of higher
formula, M x / n [ AlO 2 ] x .(SiO 2 )y .mH 2 O , where, M may be
molecular mass.
(2) Enzymes catalyse numerous reactions, simple cation like Na  , K  or Ca 2  , n is the charge on the
simple cation, m is the number of molecules of water of
especially those connected with natural processes.
crystallization.
(3) Numerous reactions occur in the bodies of
(2) Some well known zeolites are as follows,
animals and plants to maintain the life process. These
reactions are catalysed by enzymes. The enzymes are Erionite  Na2 K2CaMg(AlO2 )2 (SiO 2 )2 .6 H2O
Gemelinite  Na2Ca( AlO2 )2 (SiO 2 )4 .6 H 2O
S Surface Chemistry 581
Faujasite (natural)  Na56 ( AlO2 )56 (SiO 2 )136 .250 H 2O substances but is a state of matter like solid, liquid and
gas. Any substance can be brought into colloidal state.
ZSM-5  H x [(AlO2 )x (SiO 2 )96  x ].16 H2O
(4) The colloidal state depends on the particle
Linde-A (synthetic)  [Na12 (AlO2 )12 (SiO 2 )12 .27 H2O]8
size. If is regarded as intermediate state between true
(3) The characteristic feature of zeolites is the solution and suspension.
openness of the structure, which permits cavities of Table : 14.2 Features of the three types of solutions
different sizes.
Property Suspension Colloid True
(4) The open structure is provided by silica in which solution solution
aluminium occupies x/(x+y) fraction of the telrahedral Nature Heterogeneo Heterogeneo Homogeneo
sites. us us us
(5) The negative charge of the aluminosilicate Particle size > 100 nm 1 nm – 100 < 1 nm
framework is neutralized by the replaceable cations. nm
(6) The void space forms more than 50% of the Separation by
total volume, which is occupied by water molecules. (i) Ordinary Possible Not possible Not
filtration Possible Possible possible
(7) The reaction- selectivity of zeolites depends
(ii) Ultra- Not
upon the size of cavities (cages), pores (apertures) and
filtration possible
the distribution of pores in the structure. The pore size
Settling of Settle under Settle only Do not
in zeolites generally varies from 260 pm to 740 pm.
particles gravity on settle
(8) Zeolite have high porosity due to the presence centrifugati
of one, two, or three dimensional networks of on
interconnected channels and cavities of molecular Appearance Opaque Generally Transpare
dimensions. transparent nt
(9) There is a new class of highly siliceous Tyndall effect Shows Shows Does not
zeolites with an optimal pore diameter of 550pm. ZSM- show
5 is one such zeolite having the formula. Diffusion of Does not Diffuses Diffuses
[H x (AlO 2 ) x .(SiO 2 )96  x ].16 H 2 O particles diffuse slowly rapidly
Brownian May show Shows Negligible
(10) The zeolite catalyst ZSM-5 converts alcohols movement
to gasoline (petrol) by dehydrating the alcohol and
producing a mixture of wide variety of hydrocarbons.
Colloidal state
(1) The foundation of colloidal chemistry was laid
down by an English scientist, Thomas Graham, in 1861.
The credit for the various advances in this field goes to
eminent scientists like Tyndall, Hardy, Zsigmondy, Suspension Colloidal True
Size > 100 nm solution
Size solution
Size < 1
N.R. Dhar, S.S. Bhatnagar and others.
between nm
(2) Thomas Graham classified the soluble 1-100types
Fig. 14.1 Three nm solutions
substances into two categories depending upon the rate Phases of colloids and Their classification
of diffusion through animal and vegetable membranes (1) Phases of colloids : We know that a colloidal
or parchment paper.
solution is of heterogeneous nature. It consists of two
(i) Crystalloids : They have higher rate of phases which are as follows
diffusion and diffused from parchment paper.
(i) Internal phase or Dispersed phase
Examples : All organic acids, bases and salts and (Discontinuous phase) : It is the component present in
organic compounds such as sugar, urea etc. small proportion and is just like a solute in a solution.
(ii) Colloids (Greek word, kolla, meaning glue-like) For example in the colloidal solution of silver in water
: They have slower rate of diffusion and can not (silver acts as a dispersed phase)
diffused from parchment paper. (ii) External phase or Dispersion medium
Examples : Starch, gelatin, gums, silicic acid and (continuous phase) : It is generally component present
hdemoglobin etc. in excess and is just like a solvent in a solution. For
(3) The above classification was discarded i.e., the example, in the colloidal solution of silver in water.
terms colloid does not apply to a particular class of Water act as a dispersion medium.
 582 Surface Chemistry
(2) Classification of colloids : The colloids are Surface Lower than that of Same as that of the
classified on the basis of the following criteria tension the medium medium
Viscosity Much higher than Same as that of the
(i) Classification based on the physical state of that of the medium medium
the dispersed phase and dispersion medium : Reversibil Reversible Irreversible
Depending upon the physical state of dispersed phase ity
Stability More stable Less stable
and dispersion medium whether these are solids,
Visibility Particles can’t be Particles can be
liquids or gases, eight types of colloidal systems are detected even under detected under
possible. ultramicroscope ultramicroscope.
Table : 14.3 Different types of colloidal systems Migration Particles may Particles migrate either
migrate in either towards cathode or
Disperse Dispersio Colloidal Examples direction or do not anode in an electric
d phase n System migrate in an field because they
Medium electric field carry charge.
Liquid Gas Aerosol of Fogs, clouds, mists, because do not carry
any charge.
liquids fine insecticide
sprays Action of Addition of smaller Coagulation takes place
electrolyt quantity of
Solid Gas Aerosol of Smoke, volcanic e electrolyte has little
solids dust, haze effect
Gas Liquid Foam or Soap lather. Hydration Extensive hydration No hydration
froth Lemonade froth, takes place
foam, whipped Examples Gum, gelatin, Metals like Ag and Au,
cream, soda water starch, proteins, hydroxides like
rubber etc. Al (OH ) 3 , Fe (OH ) 3 metal
Liquid Liquid Emulsions Milk, emulsified
oils, medicines sulphides like AS 2 S 3
Solid Liquid Sols Most paints, starch etc.
in water, proteins, (iii) Classification based on types of particle of
gold sol, arsenic
dispersed phase : Depending upon the type of the
sulphide sol, ink
particles of the dispersed phase, the colloids are
Gas Solid Solid foam Pumice stone,
classified as follows.
styrene rubber,
foam rubber (a) Multimolecular colloids
Liquid Solid Gels Cheese, butter, boot  When on dissolution, atoms or smaller
polish, jelly, curd molecules of substances (having diameter less than
Solid Solid Solid sols Ruby glass, some 1nm) aggregate together to form particles of colloidal
(coloured gem stones and dimensions, the particles thus formed are called
glass) alloys multimolecular colloids.
 In these sols the dispersed phase consists of
(ii) Classification based on Nature of interaction aggregates of atoms or molecules with molecular size
between dispersed phase and dispersion medium: less than 1 nm.
Depending upon the nature of interactions between  For example, sols of gold atoms and sulphur
dispersed phase and the dispersion medium, the (S 8 ) molecules. In these colloids, the particles are held
colloidal solutions can be classified into two types as together by Vander Waal's forces. They have usually
(a) Lyophilic and (b) Lyophobic sols. lyophilic character.
(a) Lyophilic colloids (water loving) : “The (b) Macromolecular colloids
colloidal solutions in which the particles of the  These are the substances having big size
dispersed phase have a great affinity for the dispersion molecules (called macromolecules) which on
dissolution form size in the colloidal range. Such
medium, are called lyophilic collodis.”
substances are called macromolecular colloids.
(b) Lyophobic colloids (water hateing) : “The  These macromolecules forming the dispersed
colloidal solutions in which there is no affinity between phase are generally polymers having very high
particles of the dispersed phase and the dispersion molecular masses.
medium are called lyophobic colloids.”  Naturally occurring macromolecules are starch,
Distinction between lyophilic and lyophobic sols cellulose, proteins, enzymes, gelatin etc. Artificial
macromolecules are synthetic polymers such as nylon,
Property Lyophilic sols Lyophobic sols
(suspensoid) (Emulsoid)
polythene, plastics, polystyrene etc.
S Surface Chemistry 583
 They have usually lyophobic character.  Some other examples of micelles are sodium
(c) Associated colloids palmitate (C15 H31COONa ) , Sodium lauryl sulphate
 These are the substances which on dissolved in [CH 3 (CH 2 )11 SO 3 O  Na  ] , Cetyl trimethyl ammonium
a medium behave as normal electrolytes at low  
concentration but behave, as colloidal particles at bromide CH 3 (CH 2 )15 (CH 2 )3 N Br etc.
higher concentration due to the formation of General methods of preparation of colloids
aggregated particles. The aggregates particles thus
formed are called micelles. Lyophilic and lyophobic colloidal solutions (or
sols) are generally prepared by different types of
 Their molecules contain both lyophilic and
lyophobic groups. methods. Some of the common methods are as follows.
Micelles (1) Preparation of Lyophilic colloids
 Micelles are the cluster or aggregated particles (i) The lyophilic colloids have strong affinity
formed by association of colloid in solution. between particles of dispersed phase and dispersion
 The common examples of micelles are soaps medium.
and detergents.
(ii) Simply mixing the dispersed phase and
 The formation of micelles takes place above a dispersion medium under ordinary conditions readily
particular temperature called Kraft temperature forms these colloidal solutions.
(Tk ) and above a particular concentration called critical
(iii) For example, the substance like gelatin, gum,
micellization concentration (CMC).
starch, egg, albumin etc. pass readily into water to give
 They are capable of forming ions. colloidal solution.
 Micelles may contain as many as 100 molecules
(iv) They are reversible in nature become these
or more.
can be precipitated and directly converted into colloidal
 For example sodium stearate (C17 H 35 COONa ) is a
state.
typical example of such type of molecules.
(2) Preparation of Lyophobic colloids :
 When sodium stearate is dissolved in water, it Lyophobic colloids can be prepared by mainly two types
gives Na  and C 17 H 35 COO  ions. of methods.
 
C17 H 35 COONa  C17 H 35 COO  Na (i) Condensation method : In these method,
Sodium stearate Stearate ion
smaller particles of dispersed phase are condensed
The stearate ions associate to form ionic suitably to be of colloidal size. This is done by the
micelles of colloidal size. following methods.
 It has long hydrocarbon part of C17 H 35 radical.
(a) By oxidation : A colloidal solution of sulphur
Which is lyophobic and COO  part which is lyophilic. can be obtained by bubbling oxygen (or any other
 In the figure, the chain corresponds to stearate oxidising agent like HNO 3 , Br2 etc.) through a solution
ion, (C17 H 35 COO  ) . When the concentration of the of hydrogen sulphide in water.
solution is below from its CMC (10 3 mol L1 ) , it behaves 2 H 2 S  O2 (or any other oxidising agent)  2 H 2 O  2 S
as normal electrolyte. But above this concentration it is (b) By reduction : A number of metals such as
aggregated to behave as micelles.
silver, gold and platinum, have been obtained in
– colloidal state by treating the aqueous solution of their
Na+
– Na+ – salts, with a suitable reducing agent such as
Na+
formaldehyde, phenyl hydrazine, hydrogen peroxide,
Na+ stannous chloride etc.
Na+ – –

2 AuCl 3  3 SnCl 2  3 SnCl 4  2 Au

Gold sol
Na+
– –
Na+
2 AuCl 3  3 HCHO  3 H 2 O  2 Au  3 HCOOH  6 HCl
– Na+ Gold sol
Fig. 14.2 Aggregation of several ions to form ionic The gold sol, thus prepared, has a purple colour
micelle
and is called purple of cassius.
 The main function of a soap is to reduce oily
and greasy dirt to colloidal particles (an emulsion). (c) By hydrolysis : Many salt solutions are rapidly
Soap therefore, are known as emulsifying agents. hydrolysed by boiling dilute solutions of their salts. For
example, ferric hydroxide and aluminium hydroxide
 584 Surface Chemistry
sols are obtained by boiling solutions of the  This method is Metal
corresponding chlorides. used to prepare sols of electrode
platinum, silver, copper s
FeCl 3  3 H 2 O  Fe(OH )3  3 HCl Arc
Colloidal sol or gold.
 The metal whose ice
Similarly silicic acid sol is obtained by the Water
sol is to be prepared is
hydrolysis of sodium silicate.
made as two electrodes
(d) By double decomposition : A sol of arsenic which immerged in Fig. 14.4 Bredig's arc
sulphide is obtained by passing hydrogen sulphide dispersion medium such method
through a cold solution of arsenious oxide in water. as water etc.
As 2 O 3  3 H 2 S  As 2 S 3  3 H 2 O  The dispersion medium is kept cooled by ice.
 An electric arc is struck between the electrodes.
(e) By excessive cooling : A colloidal solution of
ice in an organic solvent like ether or chloroform can  The tremendous heat generate by this method
be prepared by freezing a solution of water in the and give colloidal solution.
solvent. The molecules of water which can no longer be  The colloidal solution prepared is stabilised by
held in solution, separately combine to form particles adding a small amount of KOH to it.
of colloidal size. (c) By peptisation
(f) By exchange of solvent : Colloidal solution of  The process of converting a freshly prepared
certain substances such as sulphur, phosphorus, which precipitate into colloidal form by the addition of
are soluble in alcohol but insoluble in water can be suitable electrolyte is called peptisation.
prepared by pouring their alcoholic solution in excess  The electrolyte is used for this purpose is called
of water. For example, alcoholic solution of sulphur on peptizing agent or stabilizing agent.
pouring into water gives milky colloidal solution of  Cause of peptisation is the adsorption of the
sulphur. ions of the electrolyte by the particles of the
(g) By change of physical state : Sols of substances precipitate.
like mercury and sulphur are prepared by passing their  Important peptizing agents are sugar, gum,
vapour’s through a cold water containing a suitable gelatin and electrolytes.
stabilizer such as ammonium salt or citrate.  Freshly prepared ferric hydroxide can be
(ii) Dispersion methods : In these methods, converted into colloidal state by shaking it with water
larger particles of a substance (suspensions) are containing Fe 3  or OH  ions, viz. FeCl 3 or
broken into smaller particles. The following methods NH 4 OH respectively.
are employed.
Fe(OH )3  FeCl 3  [Fe(OH )3 Fe]3   3Cl 
(a) Mechanical dispersion Precipitate electrolyte Colloidal sol

 In this method, Suspension +

+
+ +
+
+ +
+
+
the substance is first Driving Belt 3+
Fe(OH) + Fe + + + + + +
ground to coarse
3 + + + + + +
particles. Discharge Discharge From + + +
Precipitate electrolyte Colloidal particles
 It is then of Fe(OH)3 FeCl of Fe(OH)3
mixed with the Metal disc
3

dispersion medium to Fig. 14.5 Preparation of colloidal sol by

Fig. 14.3 Colloidal mill peptisation
get a suspension.  A stable sol of stannic oxide is obtained by
 The suspension is then grinded in colloidal mill. adding a small amount of dilute HCl to stannic oxide
 It consists of two metallic discs nearly touching precipitates.
each other and rotating in opposite directions at a very  Similarly, a colloidal solution of Al(OH )3 and
high speed about 7000 revolution per minute. AgCl are obtained by treating the corresponding
 The space between the discs of the mill is so freshly prepared precipitate with very dilute solution
adjusted that coarse suspension is subjected to great of HCl and AgNO 3 or KCl respectively.
shearing force giving rise to particles of colloidal size.
Purification of colloidal solution
 Colloidal solutions of black ink, paints,
varnishes, dyes etc. are obtained by this method. The following methods are commonly used for
(b) By electrical dispersion or Bredig’s arc method the purification of colloidal solutions.
S Surface Chemistry 585
(1) Dialysis (1) Physical properties
(i) The process of separating the particles of (i) Heterogeneous nature : Colloidal sols are
colloid from those of crystalloid, by means of diffusion heterogeneous in nature. They consists of two phases;
through a suitable membrane is called dialysis. the dispersed phase and the dispersion medium.

(ii) It’s principle is based upon the fact that (ii) Stable nature : The colloidal solutions are
colloidal particles can not pass through a parchment or quite stable. Their particles are in a state of motion and
cellophane membrane while the ions of the electrolyte do not settle down at the bottom of the container.
can pass through it. (iii) Filterability : Colloidal particles are
(iii) The impurities slowly diffused out of the bag readily passed through the ordinary filter papers.
leaving behind pure colloidal solution However they can be retained by special filters
(iv) The distilled water is changed frequently to known as ultrafilters (parchment paper).
avoid accumulation of the crystalloids otherwise they
may start diffusing back into the bag. (2) Colligative properties
(v) Dialysis can be used for removing HCl from (i) Due to formation of associated molecules,
the ferric hydroxide sol. observed values of colligative properties like relative
(2) Electrodialysis decrease in vapour pressure, elevation in boiling point,
depression in freezing point, osmotic pressure are
(i) The ordinary process of dialysis is slow. smaller than expected.
(ii) To increase the process of purification, the (ii) For a given colloidal sol the number of
dialysis is carried out by applying electric field. This particles will be very small as compared to the true
process is called electrodialysis. solution.
(iii) The important application of electrodialysis (3) Mechanical properties
process in the artificial kidney machine used for the (i) Brownian movement
purification of blood of the patients whose kidneys
(a) Robert Brown, a botanist discovered in 1827
have failed to work. The artificial kidney machine
that the pollen grains suspended in water do not
works on the principle of dialysis.
remain at rest but move about continuously and
(3) Ultra – filtration randomly in all directions.
(i) Sol particles directly pass through ordinary (b) Later on, it was observed that the colloidal
filter paper because their pores are larger (more than particles are moving at random in a zig – zag motion.
1  or 1000 m  ) than the size of sol particles (less than This type of motion is called Brownian movement.
200 m  ). (c) The molecules of the dispersion medium are
constantly colloiding with the particles of the dispersed
(ii) If the pores of the ordinary filter paper are
phase. It was stated by Wiener in 1863 that the impacts
made smaller by soaking the filter paper in a solution
of the dispersion medium particles are unequal, thus causing
of gelatin of colloidion and subsequently hardened by
a zig-zag motion of the dispersed phase particles.
soaking in formaldehyde, the treated filter paper may
retain colloidal particles and allow the true solution (d) The Brownian movement explains the force of
particles to escape. Such filter paper is known as ultra gravity acting on colloidal particles. This helps in
- filter and the process of separating colloids by using providing stability to colloidal sols by not allowing
ultra – filters is known as ultra – filtration. them to settle down.

(4) Ultra – centrifugation (ii) Diffusion : The sol particles diffuse from
higher concentration to lower concentration region.
(i) The sol particles are prevented from setting
However, due to bigger size, they diffuse at a lesser
out under the action of gravity by kinetic impacts of the
speed.
molecules of the medium.
(ii) The setting force can be enhanced by using (iii) Sedimentation : The colloidal particles settle
high speed centrifugal machines having 15,000 or more down under the influence of gravity at a very slow rate.
revolutions per minute. Such machines are known as This phenomenon is used for determining the molecular
ultra–centrifuges. mass of the macromolecules.

Properties of colloidal solutions (4) Optical properties : Tyandall effect

(i) When light passes through a sol, its path
The main characteristic properties of colloidal
becomes visible because of scattering of light by particles.
solutions are as follows.
 586 Surface Chemistry
It is called Tyndall effect. This phenomenon was studied (a) The electrical properties of colloids can also
for the first time by Tyndall. The illuminated path of the be explained by electrical double layer theory.
beam is called Tyndall cone. According to this theory a double layer of ions appear
(ii) The intensity of the scattered light depends on at the surface of solid.
the difference between the refractive indices of the (b) The ion preferentially adsorbed is held in
dispersed phase and the dispersion medium. fixed part and imparts charge to colloidal particles.
(iii) In lyophobic colloids, the difference is (c) The second part consists of a diffuse mobile
appreciable and, therefore, the Tyndall effect is well - layer of ions. This second layer consists of both the type
defined. But in lyophilic sols, the difference is very of charges. The net charge on the second layer is exactly
small and the Tyndall effect is very weak. equal to that on the fixed part.
(iv) The Tyndall effect confirms the (d) The existence of opposite sign on fixed and
heterogeneous nature of the colloidal solution. diffuse parts of double layer leads to appearance of a
difference of potential, known as zeta potential or
(v) The Tyndall effect has also been observed by
electrokinetic potential. Now when electric field is
an instrument called ultra – microscope.
employed the particles move (electrophoresis)
Some example of Tyndall effect are as follows (iii) Electro-osmosis
(a) Tail of comets is seen as a Tyndall cone due to (a) In it the movement of the dispersed particles
the scattering of light by the tiny solid particles left by the are prevented from moving by semipermeable
comet in its path. membrane.
(b) Due to scattering the sky looks blue. (b) Electro-osmosis is a phenomenon in which
(c) The blue colour of water in the sea is due to dispersion medium is allowed to move under the
scattering of blue light by water molecules. influence of an electrical field, whereas colloidal
particles are not allowed to move.
(d) Visibility of projector path and circus light.
(c) The existence of electro-osmosis has suggested
(e) Visibility of sharp ray of sunlight passing
that when liquid forced through a porous material or a
through a slit in dark room.
capillary tube, a potential difference is setup between
(5) Electrical properties the two sides called as streaming potential. So the
(i) Electrophoresis reverse of electro-osmosis is called streaming
potential.
(a) The phenomenon of movement of colloidal
particles under an applied electric field is called Origin of the charge on colloidal particles
electrophoresis. The origin of the charge on the sol particles in
(b) If the particles accumulate near the negative most cases is due to the preferential adsorption of
electrode, the charge on the particles is positive. either positive or negative ions on their surface. The
(c) On the other hand, if the sol particles sol particles acquire electrical charge in any one or
accumulate near the positive electrode, the charge on more of the following ways.
the particles is negative. (1) Due to the dissociation of the surface
molecules : Some colloidal particles develope electrical
(d) The apparatus consists of a U-tube with two
charge due to the dissociation / ionisation of the
Pt-electrodes in each limb.
surface molecules. The charge on the colloidal particles
(e) When electrophoresis of a sol is carried out is balanced by the oppositely charged ions in the sol.
with out stirring, the bottom layer gradually becomes For example, an aqueous solution of soap (sodium
more concentrated while the top layer which contain palmitate) which dissociates into ions as,
pure and concentrated colloidal solution may be
C15 H 31 COONa  C15 H 31 COO   Na 
decanted. This is called electro decanation and is used Sodium palmitate
for the purification as well as for concentrating the sol. The cations (Na+) pass into the solution while the
(f) The reverse of electrophoresis is called anions (C15 H 31 COO  ) have a tendency to form aggregates
Sedimentation potential or Dorn effect. The
due to weak attractive forces present in the
sedimentation potential is setup when a particle is hydrocarbon chains.
forced to move in a resting liquid. This phenomenon
(2) Due to frictional electrification
was discovered by Dorn and is also called Dorn effect.
(i) It is believed that the frictional electrification
(ii) Electrical double layer theory due to the rubbing of the dispersed phase particles with
S Surface Chemistry 587
that of dispersion medium results in some charge on Stability of sols
the colloidal particles.
Sols are thermodynamically unstable and the
(ii) The dispersion medium must also get some dispersed phase (colloidal particles) tend to separate
charge, because of the friction. Since it does not carry out on long standing due to the Vander Waal's
any charge, the theory does not seem to be correct. attractive forces. However sols tend to exhibit some
(3) Due to selective adsorption of ions stability due to
(i) The particles constituting the dispersed phase (1) Stronger repulsive forces between the
adsorb only those ions preferentially which are similarly charged particles
common with their own lattice ions. (2) Particle-solvent interactions : Due to strong
(ii) For example, when a small quantity of silver particle-solvent (dispersion medium) interactions, the
nitrate ( AgNO 3 ) solution is added to a large quantity of colloidal particles get strongly solvated.
potassium iodide (KI) solution, the colloidal particles of Coagulation or Flocculation or Precipitation
silver iodide adsorb I  from the solution to become
“The phenomenon of the precipitation of a colloidal
negatively charged, (at this stage KI is in excess, and solution by the addition of the excess of an electrolyte is
I  being common to AgI ) called coagulation or flocculation.”
AgI  I  ( AgI )I  The coagulation of the lyophobic sols can be
(Colloidal (in excess (Colloidal particle
particle ) in the becomes positivel y carried out by following methods.
medium) charged)
(1) By electrophoresis : In electrophoresis the
But, when a small quantity of potassium iodide colloidal particles move towards oppositely charged
(KI) solution is added to a large quantity of silver electrode. When these come in contact with the
nitrate solution ( AgNO 3 ) ; the colloidal silver iodide electrode for long these are discharged and
precipitated.
particles adsorb Ag  from the solution to become
(2) By mixing two oppositely charged sols :
positively charged, (at this stage AgNO 3 is in excess
When oppositely charged sols are mixed in almost
and Ag  is common to AgI ), equal proportions, their charges are neutralised. Both
AgI  Ag   ( AgI )Ag  sols may be partially or completely precipitated as the
(Colloidal (in excess in (Colloidal particle mixing of ferric hydroxide (+ve sol) and arsenious
particle ) the medium) becomes positivel y
charged) sulphide (–ve sol) bring them in precipitated form. This
Ag+
I– type of coagulation is called mutual coagulation or
Ag+ – – – Ag
+ –
I– + + + I meteral coagulation.
– AgI – + AgI +
– (3) By boiling : When a sol is boiled, the adsorbed
– + +
Ag+ – – Ag +
I– + + I– layer is disturbed due to increased collisions with the
Ag+ I– molecules of dispersion medium. This reduces the
I– ions remain in dispersion
Ag+ ions remain in dispersed charge on the particles and ultimately they settle down
medium (Agl, I– Sol) medium (Agl, Ag+ Sol)
to form a precipitate.
Fig. 14.6
(4) By persistent dialysis : On prolonged
(iii) Depending upon the nature of charge on the dialysis, the traces of the electrolyte present in the sol
particles of the dispersed phase, the colloidal solutions are removed almost completely and the colloids become
are classified into positively charged and negatively unstable.
charged colloids. Some typical examples are as follows (5) By addition of electrolytes : The particles of
(a) Negatively charged (b) Positively charged the dispersed phase i.e., colloids bear some charge.
colloids colloids When an electrolyte is added to sol, the colloidal
 Metal sulphides :  Metal hydroxides : particles take up ions carrying opposite charge from
As 2 S 3 , CdS Al(OH )3 , Fe(OH )3 the electrolyte. As a result, their charge gets
 Metal dispersions :  Metal oxide : TiO 2 neutralised and this causes the uncharged, particles to
Ag, Au, Pt come closer and to get coagulated or precipitated. For
 Basic dyes : Methylene
example, if BaCl 2 solution is added to As 2 S 3 sol the
 Acid dyes : Eosin, congo blue
red  Haemoglobin Ba 2  ions are attracted by the negatively charged sol
 Sols of starch, gums,  Sulphur sol particles and their charge gets neutralised. This lead to
gold, coagulation.
gelatin etc. (6) Hardy schulze rule : The coagulation capacity
of different electrolytes is different. It depends upon
 588 Surface Chemistry
the valency of the active ion are called flocculating ion, Thus, lyophilic colloids can prevent the coagulation of
which is the ion carrying charge opposite to the charge any lyophobic sol.
on the colloidal particles. “According to Hardy Schulze “The phenomenon of preventing the coagulation of
rule, greater the valency of the active ion or flocculating a lyophobic sol due to the addition of some lyophilic
ion, greater will be its coagulating power” thus, Hardy colloid is called sol protection or protection of colloids.”
Schulze law state:  The protecting power of different protective
(i) The ions carrying the charge opposite to that of (lyophilic) colloids is different. The efficiency of any
sol particles are effective in causing coagulation of the protective colloid is expressed in terms of gold
sol. number.
(ii) Coagulating power of an electrolyte is directly Gold number : Zsigmondy introduced a term
proportional to the valency of the active ions (ions called gold number to describe the protective power of
causing coagulation). different colloids. This is defined as, “weight of the
For example to coagulate negative sol of As 2 S 3 , dried protective agent in milligrams, which when added
to 10 ml of a standard gold sol (0.0053 to 0.0058%) is
the coagulation power of different cations has been
just sufficient to prevent a colour change from red to
found to decrease in the order as, Al 3   Mg 2   Na 
blue on the addition of 1 ml of 10 % sodium chloride
Similarly, to coagulate a positive sol such as solution, is equal to the gold number of that protective
Fe(OH )3 , the coagulating power of different anions has colloid.”
been found to decrease in the order : Thus, smaller is the gold number, higher is the
4
[Fe(CN )6 ]  PO 43   SO 42   Cl  protective action of the protective agent.
1
(7) Coagulation or flocculation value Protective power 
Gold number
“The minimum concentration of an electrolyte
Table : 14.4 Gold numbers of some hydrophilic
which is required to cause the coagulation or
flocculation of a sol is known as flocculation value.” substances

or Hydrophili Gold Hydrophilic Gold

c number substance number
“The number of millimoles of an electrolyte substance
required to bring about the coagulation of one litre of a Gelatin 0.005 - Sodium oleate 0.4 – 1.0
colloidal solution is called its flocculation value.” 0.01
Coagulation value or flocculating value Sodium 0.01 Gum tragacanth 2
1 caseinate

Coagulatin g power Hamoglobi 0.03 – 0.07 Potato starch 25
n
(8) Coagulation of lyophilic sols
Gum arabic 0.15 – 0.25
(i) There are two factors which are responsible
for the stability of lyophilic sols. Congo rubin number : Ostwald introduced congo
(ii) These factors are the charge and solvation of rubin number to account for protective nature of
the colloidal particles. colloids. It is defined as “the amount of protective
colloid in milligrams which prevents colour change in
(iii) When these two factors are removed, a
100 ml of 0.01 % congo rubin dye to which 0.16 g
lyophilic sol can be coagulated.
equivalent of KCl is added.”
(iv) This is done (i) by adding electrolyte (ii) and
Mechanism of sol protection
by adding suitable solvent.
(v) When solvent such as alcohol and acetone are (i) The actual
added to hydrophilic sols the dehydration of dispersed mechanism of sol Lyophilic
protectin
phase occurs. Under this condition a small quantity of protection is very
Lyophobi g
electrolyte can bring about coagulation. complex. However it may c particles
Protection of colloids and Gold number be due to the adsorption particles
 Lyophilic sols are more stable than of the protective colloid
on the lyophobic sol Fig. 14.7 Protection of
lyophobic sols. colloids
particles, followed by its solvation. Thus it stabilises
 Lyophobic sols can be easily coagulated by
the sol via solvation effects.
the addition of small quantity of an electrolyte.
 When a lyophilic sol is added to any lyophobic (ii) Solvation effects contribute much towards the
sol, it becomes less sensitive towards electrolytes. stability of lyophilic systems. For example, gelatin has
a sufficiently strong affinity for water. It is only
S Surface Chemistry 589
because of the solvation effects that even the addition emulsions. Butter and cold cream are typical examples
of electrolytes in small amounts does not cause any of this types of emulsions. Other examples are cod liver
flocculation of hydrophilic sols. However at higher oil etc.
concentration, precipitation occurs. This phenomenon (2) Properties of emulsion
is called salting out.
(i) Emulsions show all the characteristic
(iii) The salting out efficiency of an electrolyte properties of colloidal solution such as Brownian
depends upon the tendency of its constituents ions to get movement, Tyndall effect, electrophoresis etc.
hydrated i.e, the tendency to squeeze out water initially
(ii) These are coagulated by the addition of
fied up with the colloidal particle.
electrolytes containing polyvalent metal ions indicating
(iv) The cations and the anions can be arranged in the negative charge on the globules.
the decreasing order of the salting out power, such an (iii) The size of the dispersed particles in
arrangement is called lyotropic series. emulsions in larger than those in the sols. It ranges
Cations from 1000 Å to 10,000 Å. However, the size is smaller
2
: Mg  Ca 2   Sr 2   Ba 2   Li   Na   K  than the particles in suspensioins.
 NH 4   Rb   Cs  (iv) Emulsions can be converted into two separate
liquids by heating, centrifuging, freezing etc. This
Anions : Citrate3   SO 4 2   Cl   NH 3   I   CNS  process is also known as demulsification.
Ammonium sulphate, due to its very high (3) Applications of emulsions
solubility in water, is oftenly used for precipitating (i) Concentration of ores in metallurgy
proteins from aqueous solutions. (ii) In medicine (Emulsion water-in-oil type)
(v) The precipitation of lyophilic colloids can also (iii) Cleansing action of soaps.
be affected by the addition of organic solvents of non- (iv) Milk, which is an important constituent of
electrolytes. For example, the addition of acetone or our diet an emulsion of fat in water.
alcohol to aqueous gelatin solution causes precipitation (v) Digestion of fats in intestine is through
of gelatin. Addition of petroleum ether to a solution of emulsification.
rubber in benzene causes the precipitation of rubber.
Gels
Emulsion
(1) “A gel is a colloidal system in which a liquid is
“The colloidal systems in which fine droplets of one dispersed in a solid.”
liquid are dispersed in another liquid are called (2) The lyophilic sols may be coagulated to give a
emulsions the two liquids otherwise being mutually semisolid jelly like mass, which encloses all the liquid
immiscible.” or present in the sol. The process of gel formation is
“Emulsion are the colloidal solutions in which both called gelation and the colloidal system formed called
the dispersed phase and the dispersion medium are gel.
liquids.” (3) Some gels are known to liquify on shaking and
A good example of an emulsion is milk in which reset on being allowed to stand. This reversible sol-gel
fat globules are dispersed in water. The size of the transformation is called thixotropy.
emulsified globules is generally of the order of 10 6 m. (4) The common examples of gel are gum arabic,
Emulsion resemble lyophobic sols in some properties. gelatin, processed cheese, silicic acid, ferric hydroxide
etc.
(1) Types of Emulsion : Depending upon the
nature of the dispersed phase, the emulsions are (5) Gels may shrink by loosing some liquid help
classified as; them. This is known as synereises or weeping.
(6) Gels may be classified into two types
(i) Oil-in-water emulsions (O/W) : The emulsion
(i) Elastic gels : These are the gels which possess
in which oil is present as the dispersed phase and
the property of elasticity. They readily change their
water as the dispersion medium (continuous phase) is
shape on applying force and return to original shape
called an oil-in-water emulsion. Milk is an example of
when the applied force is removed. Common examples
the oil-in-water type of emulsion. In milk liquid fat
are gelatin, agar-agar, starch etc.
globules are dispersed in water. Other examples are,
vanishing cream etc. (ii) Non-elastic gels : These are the gels which
are rigid and do not have the property of elasticity. For
(ii) Water-in-oil emulsion (W/O) : The emulsion
example, silica gel.
in which water forms the dispersed phase, and the oil
acts as the dispersion medium is called a water-in-oil
emulsion. These emulsion are also termed oil
 590 Surface Chemistry
Application of colloids
(1) Purification of water by alum (coagulation) :
Alum which yield Al 3  ions, is added to water to
coagulate the negatively charged clay particles.
 Chemisorption and physisorption both are
(2) In rubber and tanning industry (coagulation
exothermic.
and mutual coagulation) : Several industrial processes
such as rubber plating, chrome tanning, dyeing,  Charcoal adsorbs many gases. It even adsorbs
lubrication etc are of colloidal nature polluting gases present in air in small
(i) In rubber platting, the negatively charged concentration.
particles of rubber (latex) are made to deposit on the
 The langmuir adsorption isotherm is restricted to
wires or handle of various tools by means of
the formation of unimolecular layer of gas
electrophoresis. The article on which rubber is to be
molecules on the surface of solids. However, it
deposited is made anode.
was suggested that there is possibility of
(ii) In tanning the positively charged colloidal
particles of hides and leather are coagulated by multimolecular layer of gas molecules on the
impregnating, them in negatively charged tanning surface of the solids rather than single layer on
materials (present in the barks of trees). Among the this basis Brunauer, Emmett and Teller proposed
tanning agent chromium salts are most commonly used a new theory known as B.E.T. theory.
for the coagulation of the hide material and the process
 All Bronsted acids and bases act as acid base
is called chrome tanning.
catalysts.
(3) Artificial rains : It is possible to cause
artificial rain by throwing the electrified sand or silver  The principle of electrophoresis is employed for
iodide from an aeroplane and thus coagulating the mist the separation of proteins from nucleic acids
hanging in air. removing sludge from sewage waste etc.
(4) Smoke precipitation (Coagulation) : Smoke is  Hydrophilic sols show greater stability than
a negative sol consisting of carbon particles dispersed hydrophobic sols.
in air. Thus, these particles are removed by passing
 Colloidal solution of graphite is called aquadug.
through a chamber provided with highly positively
charged metallic knob.  The phase in which the emulsifier is more soluble
becomes outer phase of the emulsion that is
(5) Formation of deltas (coagulation) : River
water consists of negatively charged clay particles of called Ben croft rule.
colloidal dimension. When the river falls into the sea,
the clay particles are coagulated by the positive
Na  , K  , Mg 2  ions etc. present in sea water and new
lands called deltas are formed.
(6) Clot formation : Blood consists of negatively
charged colloidal particles (albuminoid substance). The
colloidal nature of blood explains why bleeding stops
by applying a ferric chloride solution to the wound.
Actually ferric chloride solution causes coagulation of
blood to form a clot which stops further bleeding.
(7) Colloidal medicine : Argyrol and protargyrol
are colloidal solution of silver and are used as eye
lotions colloidal sulphur is used as disinfectant
colloidal gold, calcium and iron are used as tonics.
(8) Coating of Photographic plates : These are
thin glass plates coated with gelatin containing a fine
suspension of silver bromide. The particles of silver
bromide are colloidal in nature.