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SURFACE CHEMISTRY
2. ADSORPTION
2.4 Absorption
2.1 Definition
The phenomenon of attracting and retaining the molecules When the molecules of a substance are uniformly distributed
of a substance on the surface of a liquid or solid resulting in throughout the body of a solid or liquid, this phenomenon
The substance on the surface of which adsorption takes The phenomenon in which adsorption and absorption occur
simultaneously is called sorption. Dyes are absorbed as well
place is called adsorbent.
absorbed in cotton fibre.
Adsorbent may be a solid or a liquid. Metal powders, Adsorption is instantaneous i.e. a fast process while
powdered charcoal, animal charcoal silica powder etc. are absorption is a slow process.
commonly used as adsorbents.
Adsorbate
(gas or
Adsorbent solute)
(solid)
Adsorption Absorption
1. It is a surface phenomenon. 1. It concerns with the whole mass of the absorbent.
2. In it, the substance is only retained 2. It implies that a substance is uniformly
on the surface and does not go into distributed, through the body of the solid
the bulk or interior of the solid or or liquid.
liquid.
3. In it the concentration of the adsorbed 3. In it the concentration is low.
molecules is always greater at the
free phase.
4. It is rapid in the begining and slows 4. It occurs at the uniform rate.
down to attain equilibrium
Examples Examples
(i) Water vapours are adsorbed by (i) Water vapours are absorbed by anhydrous silica gel.
CaCl2.
(ii) NH3 is adsorbed by charcoal. (ii) NH3 is absorbed in water forming NH4OH.
(v) Decolourisation of sugar solution by
activated or animal charcoal.
(vi) Ink is adsorbed by blotting paper.
Adsorption can be classified into two categories as described existing between adsorbate particles and adsorbent are
below. almost of the same strength as chemical bonds, the
adsorption is called chemical adsorption. This type of
2.9.1 Physical adsorption : If the forces of attraction existing
a d so r p ti o n i s al so c al le d as ch em i s o rp ti o n o r
between adsorbate and adsorbent are Vander Waal’s forces,
Langmuir adsorption. This type of adsorption cannot
the adsorption is called physical adsorption. This type of
adsorption is also known as physisorption or Vander Waal’s be easily reversed.
adsorption. It can be easily reversed by heating or
decreasing the pressure.
Physisorption Chemisorption
(Vander Waal’s adsorption) (Langmuir adsorption)
1. Low heat of adsorption usually in range 1. High heat of adsorption in the range of
of 20-40 kJ/mol 50-400 kJ mol.
2. Force of attraction are Vander Waal’s forces. 2. Forces of attraction are Chemical bond forces.
3. It is reversible. 3. It is irreversible.
4. It usually takes place at low 4. It takes place at high temperature.
temperature and decreases with
increasing temperature.
5. It is related to the case of liquefication 5. It is not related.
of the gas.
6. It forms multimolecular layers. 6. It forms monomolecular layers.
7. It does not require any activation 7. It requires high activation energy.
energy.
8. High pressure is favourable. Decrease 8. High pressure is favourable. Decrease
of pressure causes desorption. of pressure does not cause desorption
9. It is not very specific. 9. It is highly specific.
Note :
Due to formation of multilayers physical adsorption decreases after some times.
Chemisorption and physisorption both are exothermic.
2.10 Factors which affect the extent of adsorption on Porous and finely powdered solid e.g. charcoal, fullers
solid surface earth, adsorb more as compared to the hard non-porous
materials. Due to this property powdered charcoal is used
The following are the factors which affect the adsorption of in gas masks used in coal mines.
gases on solid surface. Gases with high critical temperature are adsorbed at
2.10.1 Nature of the adsorbate (gas) and adsorbent (solid) higher extent as compared to gases with lower critical
temperatures.
Volumes of gases at N.T.P., adsorbed by 1g of charcoal at 288 k
2.10.2 Surface area of the solid adsorbent : The extent of 2.11.1 Freundlich adsorption isotherm : Freundlich
adsorption depends directly upon the surface area of the adsorption isotherm is obeyed by the adsorptions where
adsorbent, i.e. larger the surface area of the adsorbent, the adsorbate forms a monomolecular layer on the surface
greater is the extent of adsorption.
of the adsorbent.
2.10.3 Effect of pressure on the adsorbate gas :
1
An increase in the pressure of the adsorbate gas increases x x 1
kP n or log log k lo g P
m m n
the extent of adsorption.
where, x is the weight of the gas adsorbed by m gm of the
At low temperature, the extent of adsorption increases adsorbent at a pressure P, thus x/m represents the amount of
rapidly with pressure.
gas adsorbed by the adsorbent per gm (unit mass), k and n
At low pressure, the extent of adsorption is found to be
directly proportional to the pressure. are constant at a particular temperature and for a particular
adsorbent and adsorbate (gas), n is always greater than one,
At high pressure (closer to the saturation vapour pressure indicating that the amount of the gas adsorbed does not
of the gas), the adsorption tends to achieve a limiting value. increase as rapidly as the pressure.
At low pressure, the extent of adsorption varies linearly
x
with pressure v P1
m
At high pressure, it becomes independent of pressure
x
v P0
m
x
At moderate pressure depends upon pressure raised to
1 m
x
powers v Pn
m
x
Extent of adsorption
m
SURFACE CHEMISTRY
The physical adsorption isobar shows a decrease in x/m 2.14.4 Concentration of the solute in the solution.
throughout with rise in temperature, the chemisorption isobar
2.15 Positive and Negative Adsorption
shows an initial increase with temperature and then the
expected decrease. The initial increase is because of the fact In case of adsorption by solids from the solutions, mostly
the solute is adsorbed on the surface of the solid adsorbent
that the heat supplied acts as activation energy required in
so that concentration of solute on the surface of the
chemisorption (like chemical reactions).
adsrobent is greater than in the bulk. However in some cases.
2.13 Adsorption from Solutions the solvent from the solution may be adsorbed by the
Solid surfaces can also adsorb solutes from solutions. A few adsorbent so that the concentration of the solution increases
examples are : as compared to initial concentration.
When the concentration of the adsorbate is more on the
When litmus solution is shaken with charcoal, it becomes
surface of the adsorbent than in the bulk, it is called positive
colour less because the dye of the litmus solution is adsorbed
adsorption. If the concentration of the adsorbate increases
by charcol. in the bulk after adsorption, it is called negative adsorption.
When the colourless Mg(OH)2 is precipitated in the presence Blood solution + Conc. KCl solution o Positive adsorption
of magneson reagent (a blue coloured dye). it acquires blue Blood solution + dilute KCl solution o Negative adsorption
colour because the dye is adsorbed on the solid precipitate. 2.16 Applications of Adsorption
The extent of adsorption from solution depends upon the The phenomenon of adsorption finds a number of
concentration of the solute in the solution, and can be applications. Important applications are given as follows.
expressed by the Freundlich isotherm. The Freundlich 2.16.1 Production of high vacuum : A bulk of charcoal cooled
adsorption isotherm for the adsorption from solution is, in liquid air is connected to a vessel which has already been
1
x exhausted as for as possible by a vacuum pump. The
= kc n where, x is the mass of the solute adsorbed, m is
m
the mass of the solid adsorbent, c is the equilibrium remaining traces of air are adsorbed by the charcoal to
produce a very high vacuum.
concentration of the solute in the solution, n is a constant
2.16.2 In Gas masks : It is a device which consists of activated
having value greater than one. k is the proportionality
charcoal or a mixture of adsorbents. This apparatus is used to
constant, (The value of k depends upon the nature of solid,
adsorb poisonous gases (e.g. Cl2 , CO, oxide of sulphur etc.)
its particle size, temperature, and the nature of solute and
and thus purify the air for breathing is coal mines.
solvent etc.) The plot of x/m against c is similar to that
2.16.3 For desiccation or dehumidification : Certain
Freundlich adsorption isotherm. The above equations may substances have a strong tendency to absorb water such as
x 1
be written in the following form, log = logk + log c silica and alumina (Al2O3). These substances can be used to
m n
where c, is the equilibrium concentration of the solute in the reduce/remove water vapours or moisture present in the air.
solution. Silica gel is also used for dehumidification in electronic
equipment.
2.14 Factors affecting adsorption from solution
2.16.4 Removal of colouring matter from solution : Animal
The adsorption from solutions by solid adsorbents is found charcoal removes colours of solutions by adsorbing coloured
to depend upon the following factors : impurities. It is also used as decolouriser in the manufacture
2.14.1 Nature of the adsorbate and the adsorbent. of cane sugar.
2.16.5 Heterogeneous catalysis : Mostly heterogeneous
2.14.2 The adsorption decreases with temperature.
catalytic reactions proceed through the adsorption of
2.14.3 Greater the surface area of the adsorbent greater is gaseous reactants on solid catalyst. For example,
the adsorption.
SURFACE CHEMISTRY
Finely powdered nickel is used for the hydrogenation of 2.16.13 Chromatographic analysis : The phenomenon of
oils. adsorption has given an excellent technique of analysis
Finely divided vanadium pentaoxide (V2O5) is used in the known as chromatographic analysis. The technique finds a
contact process for the manufacture of sulphuric acid. number of applications in analytical and industrial fields.
Chromatographic technique is based on differential
Pt, Pd are used in many industrial processes as catalyst.
adsorption of different constituents of a mixture.
Manufacture of ammonia using iron as a catalyst.
2.16.14 In dyeing : Many dyes get adsorbed on the cloth
2.16.6 Separation of inert gases : Due to the difference in either directly or by the use of mordants.
degree of adsorption of gases by charcoal, a mixture of inert
“Catalyst is a substance which speeds up and speeds down a
gases can be separated by adsorption on coconut charcoal
chemical reaction without itself being used up at the end of
at different low temperatures.
the reaction and the phenomenon is known as catalysis.
2.16.7 Softening of hard water :
3.1 Types of catalysis
The hard water is made to pass through a column packed
Catalytic reactions can be broadly divided into the following types,
with zeolite (sodium aluminium silicate)
3.1.1 Homogeneous catalysis : When the reactants and the
2.16.8 De-ionisation of water :
catalyst are in the same phase (i.e. solid, liquid or gas). The
For softening water can be de-ionised by removing all catalysis is said to be homogeneous. The following are some
dissolved salts with the help of cation and anion-exchanger of the examples of homogeneous catalysis.
resin.
Oxidation of sulphur dioxide into sulphur trioxide with oxygen
2.16.9 In curing diseases : A number of drugs are adsorbed in the presence of oxides of nitrogen as the catalyst in the
on the germs and kill them or these are adsorbed on the lead chamber process.
tissues and heat them.
2 SO 2 (g) 2 (g ) o 2 SO 3 (g)
NO ( g )
The finely divided ore is added to water containing pine oil Hydrolysis of sugar is catalysed by H+ ions furnished by
and foaming agent. sulphuric acid.
H 2SO4 A
C12 H 22 O11 A H 2 O A o
The air is bubbled through the mixture. Sucrose solution C6 H12 O6 A C2 H12 O6 A
Glucose solution
The foam formed rises to the surface on which mineral
particles wetted with oil are adsorbed while earthy matter 3.1.2 Heterogeneous catalysis : The catalytic process in
settle down at the bottom. which the reactants and the catalyst are in different phases
2.16.12 In adsorption indicators : Surface of certain is known as heterogeneous catalysis. Some of the examples
precipitates such as silver halide, have the property of of heterogeneous catalysis are given below.
adsorbing some dyes like eosin, fluorescein etc. In this case Oxidation of sulphur dioxide into sulphur trioxide in the
of precipitation titrations (for example AgNO 3 Versus presence of platinum metal or vanadium pentaoxide as
NaCl) the indicator is adsorbed at the end point producing catalyst in the contact process for the manufacture of
a characteristic colour on the precipitate. sulphuric acid. The reactants are in gaseous state while the
catalyst is in solid state. 2 SO 2 (g) 2 (g) o 2 SO 3 (g )
Pt ( s )
SURFACE CHEMISTRY
Combination between nitrogen and hydrogen to form due to the formation of nitrous acid during the reaction
ammonia in the presence of finely divided iron in Haber’s which acts as an auto-catalyst.
process.
In hydrolysis of ethyl acetate, acetic acid and ethyl alcohol
N 2 (g) 3 H 2 (g ) o 2 NH 3 (g)
Fe ( s )
are formed. The reaction is initially very slow but gradually
its rate increases. This is due to formation of acetic acid
Oxidation of ammonia into nitric oxide in the presence of
which acts as an auto-catalyst in this reaction.
platinum gauze as a catalyst in Ostwald’s process.
3.1.6 Induced catalysis : When one reaction influences the
4 NH 3 (g) 5 O 2 (g ) o 4 NO (g) 6 H 2 O(g)
Pt ( s )
11 (l)
o C 6 H 12 6 (l)
H
C 12 H 22 H2 C 6 H 12 6 (l)
is added to it. Sugar Fructose Glucose
permanganate increases as the reaction progresses. This The following are the characteristics which are common to
2
acceleration is due to the presence of Mn ions most of catalytic reactions.
which are formed during reaction. Thus Mn 2 ions act as 3.2.1 A catalyst remains unchanged in mass and chemical
auto-catalyst. composition at the end of the reaction.
5H 2 C2 O4 2KMnO4 3H 2SO 4
o 3.2.2 The catalyst can not initiate the reaction: The function
of the catalyst is to alter the speed of the reaction rather
2 MnSO 4 K 2SO 4 10CO 2 8H 2 O
than to start it.
When nitric acid is poured on copper, the reaction is very 3.2.3 The catalyst is generally specific in nature: A
slow in the beginning, gradually the reaction becomes faster
substance, which acts as a catalyst for a particular reaction,
SURFACE CHEMISTRY
fails to catalyse the other reaction , different catalysts for 3.3 Theories of Catalysis
the same reactant may for different products.
3.3.1 Collision Theory of Homogeneous Catalysis :
3.2.4 The catalyst can not change the position of
According to the collision theory, a reaction occurs on
equilibrium: The catalyst catalyse both forward and
account of effective collisions between the reacting
backward reactions to the same extent in a reversible reaction
molecules. For effective collision, it is necessary that the
and thus have no effect on the equilibrium constant.
molecules must possess a minimum amount of energy known
3.2.5 Catalytic promoters : Substances which themselves as activation energy (Ea). After the collision molecules form
are not catalysts, but when mixed in small quantities with an activated complex which dissociate to yield the product
the catalysts increase their efficiency are called as promoters molecules. The catalyst provides a new pathway involving
or activators. lower amount of activation energy. Thus,
3.2.6 Catalytic poisons : Substances which destroy the
activity of the catalyst by their presence are known as Ea Ea
Ea – RT
catalytic poisons. Decreases RT
Decreases Increases
3.2.7 Change of temperature alters the rate of catalytic
reaction as it does for the same reaction in absence of
catalyst : By increasing the temperature, there is an
increase in the catalytic power of a catalyst but after a e–Ea/RT k
certain temperature its power begins to decrease. A Increases
Increases Reaction speeds up
3.3.3 Advantages of modern adsorption theory : This theory Thus, the enzyme catalysed reactions take place in two steps
can explain the following : as follows :
Small quantity of the catalyst is sufficient because the Step 1. Formation of enzyme-substrate complex.
catalyst is regenerated again and again. E S ZZX ES
YZZ (Fast and Reversible)
Enzyme Substrate Enzyme
The catalyst takes part in the reaction but is produced back Substrate complex
unchanged in mass and chemical composition at the end of Step 2. Dissociation of enzyme-substrate complex to form the
the reaction. products.
Catalytic poisons, if present, are preferentially adsorbed on ES o EP
o
the catalyst surface, thereby hindering the adsorption of Enzyme Enzyme Pr oduct
the reactant molecules. Hence, they slow down the activity Substrate complex association
of the catalyst.
E P Slow and Rate determining
This theory, however, cannot explain satisfactorily the action Enzyme Product
of catalytic promoters. Re generated
3.4 Enzyme catalysis
The rate of formation of product depends upon the
Enzymes are complex nitrogenous substances secreted by concentration of ES.
low forms of vegetables & organisms. Enzymes are actually
protein molecules of higher molecular mass. (ranging from 3.5 Activity and selectivity
15,000 – 1,000,000 g/mol) Enzymes form colloidal solutions 3.5.1 Activity : Activity is the ability of catalysts to accelerate
in water and are very effective catalysts. They catalyse chemical reactions. The degree of acceleration can be as
numerous reactions, especially those connected with natural
high as 10 10 times in certain reactions. For example reaction
processes. Numerous reactions occur in the bodies of
animals and plants to maintain the life process. These between H 2 and O 2 to form H 2 O in presence of platinum
reactions are catalysed by enzymes. The enzymes are thus, as catalyst takes place with explosive violence.
termed as bio-chemical catalysts and the phenomenon is In absence of catalyst, H2 and O2 can be stored indefinitely
known as bio-chemical catalysis. eg. without any reaction.
Nitrogenase is an enzyme present in bacteria on the root 3.5.2 Selectivity : Is the ability of catalysts to direct reaction
nodules of leguminous plants such as peas and beans, to yield particular products (excluding other).
catalyses the conversion of atmospheric N2 to NH3.
In the human body, the enzyme carbonic anhydrase catalyses
the reaction of CO2 with H2O, Pt
Example : (i) n-heptane o
CO2(aq) + H2O (l) U H+ (aq.) + HCO3 (aq.)
The forward reaction occurs when the blood takes up CO2 BiMo O4
(ii) CH3CH=CH2 o CH2 =
in the tissues, and the reverse reaction occurs when the
blood releases CO2 in lungs. 3.6 Zeolites (shape selective catalysis)
Zeolites are alumino–silicates of the general formula, Mn
[AlO2]x.(SiO2)y .mH2O, where, M may be 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 crystallization. They have
honey comb like structure called E cage. The reactions
catalyzed by zeolites depend upon the shape and size of the
reactant and product molecules. That is why these types of
reactions are called shape selective-catalysis.
SURFACE CHEMISTRY
ZSM 5
Alcohols
Dehydration o Hydrocarbons
573K
2 NO (g) O2 (g) o 2 NO2 (g)
Platinised asbestos
2 SO2 (g) O2 (g) YZZZZZZZZZ
ZZZZZZZZZZ X 2 SO3 (g)
or V2 O5 (catalyst ) Z
673723K H O(l )
SO3 (g) H2 SO4 (l ) o H2S2O7 (l )
2
o 2H2SO4 (aq)
Oleum
CO H2 H2O(g)
Fe2O3 (Catalyst )
Cr2O3 (promoter )
o CO2 (g) 2 H2 (g)
673 873K
Water gas
CuCl
4 HCl (g) O2 (g)
773K o 2H2O (l ) 2 Cl2 (g)
2
ZnO Cr2 O3
CO (g) 2 H2 (g) CH3 OH (l )
Synthesis of methanol 200 bar
432 K
4.3 Dispersed phase and Dispersion Medium solvent in a solution. For example, in the colloidal solution
of silver in water. Water acts as a dispersion medium.
4.3.1 Dispersed phase : (Discontinuous phase) : It is the
4.4 Classification of Colloids
component present in small proportion and is just like a
solute in a solution. For example in the colloidal solution of 4.4.1 Classification based on the physical state of the
silver in water (silver acts as a dispersed phase) dispersed phase and dispersion medium Depending upon
the physical state of dispersed phase and dispersion medium
4.3.2 Dispersion medium : (continuous phase) : It is
whether these are solids, liquids or gases, eight types of
generally the component present in excess and is just like a
colloidal systems are possible.
SURFACE CHEMISTRY
1. Liquid Gas Aerosol of liquids Fogs, clouds, mists, fine insecticide sprays
2. Solid Gas Aerosol of solids Smoke, volcanic dust, haze Foam or froth Soap lather.
3. Gas Liquid Lemonade froth, foam, whipped cream, soda water
4. Liquid Liquid Emulsions Milk, emulsified oils, medicines
5. Solid Liquid Sols Most paints, starch in water, proteins, gold sol, arsenic
sulphide sol, ink
6. Gas Solid Solid foam Pumice stone, styrene rubber, foam rubber
7. Liquid Solid Gels Cheese, butter, boot polish, jelly, curd
8. Solid Solid Solid sols Ruby glass, some gem stones and alloys
(coloured glass)
4.4.2 Classification based on Nature of interaction between Lyophobic colloids (water hating) : “The colloidal solutions
dispersed phase and dispersion medium : in which there is no affinity between particles of the
Lyophilic colloids (water loving) : “The colloidal dispersed phase and the dispersion medium are called
solutions in which the particles of the dispersed phase lyophobic colloids.”
have a great affinity for the dispersion medium, are called Lyophobic colloids (water hating) : “The colloidal solutions
lyophilic colloids.” in which there is no affinity between particles of the
dispersed phase and the dispersion medium are called
lyophobic colloids.”
DISTINCTION BETWEEN LYOPHILIC AND LYOPHOBIC SOLS
4.4.3 Classification based on types of particles of dispersed These macromolecules forming the dispersed phase are
phase : Depending upon the type of the particles of the generally polymers having very high molecular masses.
dispersed phase, the colloids are classified as follows. Naturally occurring macromolecules are starch, cellulose,
proteins, enzymes, gelatin etc. Artificial macromolecules
Multimolecular colloids : When on dissolution, atoms or
are synthetic polymers such as nylon, polythene, plastics,
smaller molecules of substances (having diameter less than
polystyrene etc. Their solutions are quite stable and
1nm) aggregate together to form particles of colloidal
resemble with true solution in many respects. They have
dimensions, the particles thus formed are called
usually lyophobic character. The molecules are flexible
multimolecular colloids. In these sols the dispersed phase
and can take any shape.
consists of aggregates of atoms or molecules with molecular
Associated colloids : These are the substances which
size less than 1 nm. For example, sols of gold atoms and dissolved in a medium behave as normal electrolytes at low
sulphur (S 8 ) molecules. In these colloids, the particles are concentration but behave, as colloidal particles at higher
held together by Vander Waal’s forces. They have usually concentration due to the formation of aggregated particles.
lyophilic character.
The aggregates particles thus formed are called micelles.
Macromolecular colloids : These are the substances having Their molecules contain both lyophilic and lyophobic
big size molecules (called macromolecules) which on
groups. The colloidal behaviour of such substances is due
dissolution form size in the colloidal range. Such substances
to the formation of aggregates or clusters in solutions. Such
are called macromolecular colloids.
aggregated particles are called micelles.
DIFFERENCE BETWEEN DIFFERENT TYPES OF COLLOIDS
1. They are formed by the They are molecules of large They are formed by of
aggregation of a large number size, e.g., polymers like rubber, aggergation of a large
of atoms or molecules which nylon, starch, proteins, etc. no. of ions in concen-
generally have diameters less trated solution e.g., soap
than 1 nm, e.g., sols of gold, sol.
sulphur, etc.
2. Their molecular masses are They have high molecular Their molecular masses
not very high masses. are generally high.
3. Their atoms or molecules are Due to long chain, the van der Higher is the concen-
held together by weak van der Waals forces holding them are tration, greater are the
Waals forces. comparatively stronger. van der Waals forces.
4.5.1 Cleansing action of Soaps : When oil droplet comes in As hydrophilic part is polar, these polar groups can interact
with the water molecules present around the oil droplet. As a
contact with soap solution, the stearate ions arrange
result, the oil droplet is pulled away from the surface of the
themselves around it in such a way that hydrophobic parts
cloth into water to form ionic micelle which is then washed
of the stearate ions are in the oil (or grease) and the hydrophilc.
away with the excess of water.
(a) Grease or oil on surface of cloth (b) Stearate ions arranged around the oil droplet
(c) Ionic micelle formed surrounded by sheath of negative charge.
In fact, the stearate ions of soap molecules help in making a solutions are readily formed by simply mixing the dispersed
stable emulsion of oil with water which is washed away with phase and dispersion medium under ordinary conditions.
the excess of water. It may be noted that a sheath of negative For example, the substance like gelatin, gum, starch, egg,
charge is formed around the oil globule. albumin etc. pass readily into water to give colloidal solution.
Similarly, in case of detergents, e.g., sodium lauryl sulphate, viz,
They are reversible in nature because these can be
CH3(CH2)11 OSO3 Na+, the polar group is OSO3 alongwith
precipitated and directly converted into colloidal state.
the long hydrocarbon chain. It is an example of an anionic
detergent as anions associate together to form an ionic micelle, 4.6.2 Preparation of Lyophobic colloids :
similar to that of soap. A well known example of a cationic 4.6.2.1 By oxidation : A colloidal solution of sulphur can be
detergent forming an associated colloid is that of cetyl trimethyl obtained by bubbling oxygen (or any other oxidising agent
+ – like HNO 3 , Br2 etc.) through a solution of hydrogen
ammonium bromide, CH3(CH2)15(CH3)3N Br .
4.6 General Methods of preparation of Colloids sulphide in water.
2H 2 S 2 (or any other oxidising agent) o 2 H 2 2S
Lyophilic and lyophobic colloidal solutions (or sols) are
generally prepared by different types of methods. Some of 4.6.2.2 By reduction : A number of metals such as silver,
gold and platinum, have been obtained in colloidal state by
the common methods are as follows.
treating the aqueous solution of their salts, with a suitable
4.6.1 Preparation of Lyophilic colloids : reducing agent such as formaldehyde, phenyl hydrazine,
hydrogen peroxide, stannous chloride etc.
The lyophilic colloids have strong affinity between particles
2 AuCl 3 3 SnCl 2 o 3 SnCl 4 2 Au
Gold sol
of dispersed phase and dispersion medium.These colloidal
2 AuCl 3 3 HCHO 3 H 2 o 2 Au 3 HCOOH 6 HCl
Gold sol
SURFACE CHEMISTRY
The gold sol, thus prepared, has a purple colour and is tremendous heat generates by this method and give colloidal
called purple of cassius. solution. The colloidal solution prepared is stabilised by
4.6.2.3 By hydrolysis : Many salt solutions are rapidly adding a small amount of KOH to it.
hydrolysed by boiling dilute solutions of their salts. For
example, ferric hydroxide and aluminium hydroxide sols are
obtained by boiling solutions of the corresponding
chlorides. FeCl 3 3 H 2 O o Fe(OH )3 3 HCl
Colloidal sol
Similarly silicic acid sol is obtained by the hydrolysis of
sodium silicate.
4.6.2.4 By double decomposition : A sol of arsenic sulphide
is obtained by passing hydrogen sulphide through a cold
4.6.2.7 By Peptization : The process of converting a freshly
solution of arsenious oxide in water.
prepared precipitate into colloidal form by the addition of
As 2 O 3 3 H 2 S o As 2 S 3 3 H 2
suitable electrolyte is called peptization. The electrolyte is
4.6.2.5 Mechanical dispersion : In this method, the used for this purpose is called peptizing agent or stabilizing
substance is first ground to coarse particles. It is then mixed agent. Cause of peptisation is the adsorption of the ions of
with the dispersion medium to get a suspension. The the electrolyte by the particles of the precipitate. Important
suspension is then grinded in colloidal mill. It consists of peptizing agents are sugar, gum, gelatin and electrolytes.
two metallic discs nearly touching each other and rotating Freshly prepared ferric hydroxide can be converted into
in opposite directions at a very high speed about 7000 colloidal state by shaking it with water containing Fe 3 or
revolution per minute. The space between the discs of the
OH ions, viz. FeCl 3 or NH 4 OH respectively..
mill is so adjusted that coarse suspension is subjected to
great shearing force giving rise to particles of colloidal size. Fe(OH )3 FeCl 3 o [Fe(OH )3 Fe ]3 3 Cl
Colloidal solutions of black ink, paints, varnishes, dyes etc. Precipitat e electrolyt e Colloidal sol
4.7.2 Electrodialysis : The ordinary process of dialysis is Heterogeneous nature : Colloidal sols are heterogeneous in
nature. They consists of two phases; the Dispersed Phase
slow. To increase the pace of purification, the dialysis is
and the Dispersion Medium.
carried out by applying electric field. This process is called
Stable nature : The colloidal solutions are quite stable. Their
electrodialysis. Kidneys in the human body act as dialysers
particles are in a state of motion and do not settle down at
to purify blood which is colloidal in nature. The important the bottom of the container.
application of dialysis process in the artificial kidney machine
Filterability : Colloidal particles are readily passed through
used for the purification of blood of the patients whose the ordinary filter papers. However they can be retained by
kidneys have failed to work. The artificial kidney machine special filters known as ultrafilters (parchment paper).
works on the principle of dialysis. 4.8.2 Colligative properties :
Due to formation of associated molecules, observed values
of colligative properties like relative decrease in vapour
pressure, elevation in boiling point, depression in freezing
point, osmotic pressure are smaller than expected.
For a given colloidal sol the number of particles will be very
small as compared to the true solution.
4.8.3 Mechanical properties :
Brownian movement :
The colloidal particles are moving at random in a zig – zag
motion. This type of motion is called Brownian movement.
The reason of brownian motion is that the molecules of the negative ions on their surface. The sol particles acquire
dispersion medium are constantly colloiding with the electrical charge in any one or more of the following ways.
particles of the dispersed phase. 4.9.1 Due to the dissociation of the surface molecules:
Diffusion : The sol particles diffuse from higher concentration Some colloidal particles develop electrical charge due to the
to lower concentration region. However, due to bigger size, dissociation / ionisation of the surface molecules. The charge
they diffuse at a lesser speed.
on the colloidal particles is balanced by the oppositely
Sedimentation : The colloidal particles settle down under charged ions in the sol. For example, an aqueous solution of
the influence of gravity at a very slow rate. This
soap (sodium palmitate) which dissociates into ions
phenomenon is used for determining the molecular mass of
as, C 15 H 31 COONa U C 15 H 31 COO Na .
the macromolecules. Sodium palmitate
The cations (Na+) pass into the solution while the anions
4.8.4 Optical properties : Tyandall effect :
(C 15 H 31 COO ) have a tendency to form aggregates due
When light passes through a sol, its path becomes visible
to weak attractive forces present in the hydrocarbon chains.
because of scattering of light by particles. It is called Tyndall
effect. This phenomenon was studied for the first time by 4.9.2 Due to frictional electrification : It is believed that
Tyndall. The illuminated path of the beam is called Tyndall the frictional electrification due to the rubbing of the
cone. In a true solution, there are no particles of sufficiently dispersed phase particles with that of dispersion medium
large diameter to scatter light and hence no Tyndall effect
results in some charge on the colloidal particles. The
is observed. The Tyndall effect has also been observed by
dispersion medium must also get some charge, because of
an instrument called ultra – microscope.
the friction. Since it does not carry any charge, the theory
does not seem to be correct.
3+
Ferric hydroxide colloidal particles develop negative charge 4.10.2 Electro-osmosis : In it the movement of the dispersed
due to adsorption of either OH or particles is prevented from moving by semipermeable
Fe(OH)3 +OH o Fe(OH)3 OH
– –
membrane. Electro-osmosis is a phenomenon in which
(Colloidal (in excess) (Negatively charged ferric
particle) hydroxide collodial particle) dispersion medium is allowed to move under the influence
of an electrical field, whereas colloidal particles are not
Fe(OH)3 +Cl – o Fe(OH)3 Cl – allowed to move. The existence of electro-osmosis has
(Collodial (in excess) (Negatively charged ferric
particle) hydroxide collodial particle) suggested that when liquid is forced through a porous
4.10 Electrophoresis material or a capillary tube, a potential difference is setup
between the two sides called as streaming potential.
The phenomenon of movement of colloidal particles under
an applied electric field is called electrophoresis. If the
particles accumulate near the negative electrode, the charge
on the particles is positive. On the other hand, if the sol
particles accumulate near the positive electrode, the charge
on the particles is negative.
4.11.2 Particle-solvent interactions :Due to strong particle- result, their charge gets neutralised and this causes the
solvent (dispersion medium) interactions, the colloidal
uncharged, particles to come closer and to get coagulated
particles get strongly solvated. Due to solvation, the
or precipitated. For example, if BaCl 2 solution is added to
effective distance between the colloidal particles increases,
As2S3 sol the Ba2+ ions are attracted by the negatively
and therefore, the Vander Waal’s force of attraction
charged sol particles and their charge gets neutralised. This
decreases. As a result, the particles are not able to form
leads to coagulation.
aggregates. Lyophilic sols are mainly stabilized by solvation
effects due to strong interactions between the sol particles 4.12.6 Hardy schulze rule :
and the dispersion medium. The coagulation capacity of different electrolytes is different.
4.12 Coagulation or Flocculation or Precipitation It depends upon the valency of the active ion are called
flocculating ion, which is the ion carrying charge opposite
“The phenomenon of the precipitation of a colloidal to the charge on the colloidal particles. Greater the valency
solution by the addition of the excess of an electrolyte is of the active ion or flocculating ion, greater will be its
called coagulation or flocculation.” coagulating power”.
4.12.1 By electrophoresis : In electrophoresis the colloidal Coagulating power of an electrolyte is directly
particles move towards oppositely charged electrode. When proportional to the valency of the active ions (ions causing
these come in contact with the electrode for long these are coagulation).
discharged and precipitated.
For example to coagulate negative sol of As2 S3 , the
4.12.2 By mixing two oppositely charged sols : When coagulation power of different cations has been found to
oppositely charged sols are mixed in almost equal decrease in the order as, Al3 ! Mg 2 ! Na
proportions, their charges are neutralised. Both sols may be
Similarly, to coagulate a positive sol such as Fe(OH)3, the
partially or completely precipitated as the mixing of ferric
coagulating power of different anions has been found to
hydroxide (+ve sol) and arsenious sulphide (–ve sol) brings
decrease in the order :
them in precipitated form. This type of coagulation is called
[Fe(CN)6 ]4 ! PO34 ! SO24 ! Cl
mutual coagulation or meteral coagulation.
4.12.7 Coagulation or flocculation value :
4.12.3 By boiling : When a sol is boiled, the adsorbed layer
“The minimum concentration of an electrolyte which is
is disturbed due to increased collisions with the molecules
required to cause the coagulation or flocculation of a sol
of dispersion medium. This reduces the charge on the
is known as flocculation value.”
particles and ultimately they settle down to form a precipitate.
or
4.12.4 By persistent dialysis : On prolonged dialysis, the
traces of the electrolyte present in the sol are removed almost “The number of millimoles of an electrolyte required to
completely and the colloids become unstable. bring about the coagulation of one litre of a colloidal
solution is called its flocculation value.”
4.12.5 By addition of electrolytes : The particles of the
dispersed phase i.e., colloids bear some charge. When an Thus , a more efficient flocculating agent shall have lower
electrolyte is added to sol, the colloidal particles take up flocculating value.
ions carrying opposite charge from the electrolyte. As a
SURFACE CHEMISTRY
1
Note : Coagulating value or flocculating value v .
coag ulating po w er
4.12.8 Coagulation of lyophilic sols : There are two factors 4.13.1 Gold number : Zsigmondy introduced a term called
which are responsible for the stability of lyophilic sols. These gold number to describe the protective power of different
colloids. This is defined as, “weight of the dried protective
factors are the charge and solvation of the colloidal particles.
agent in milligrams, which when added to 10 ml of a
When these two factors are removed, a lyophilic sol can be
standard gold sol (0.0053 to 0.0058%) is just sufficient to
coagulated. This is done by adding electrolyte and by adding
prevent a colour change from red to blue on the addition
suitable solvent. When solvent such as alcohol and acetone
of 1 ml of 10 % sodium chloride solution, is equal to the
are added to hydrophilic sols the dehydration of dispersed
gold number of that protective colloid.”
phase occurs. Under this condition a small quantity of
electrolyte can bring about coagulation.
The protective colloids play very significant role in 4.14.4 Smoke precipitation (Coagulation) : Smoke is a
stabilisation of the non–aqueous dispersions, such as paints, negative sol consisting of carbon particles dispersed in air.
printing inks etc. Thus, these particles are removed by passing through a
4.13.2 Congo rubin number : Ostwald introduced congo chamber provided with highly positively charged metallic
rubin number to account for protective nature of colloids. It knob.
is defined as “the amount of protective colloid in milligrams 4.14.5 Formation of deltas (Coagulation) : River water
which prevents colour change in 100 ml of 0.01 % congo consists of negatively charged clay particles of colloidal
rubin dye to which 0.16 g equivalent of KCl is added.” dimension. When the river falls into the sea, the clay particles
are coagulated by the positive Na , K , Mg 2 ions etc.
4.14 Application of colloids
present in sea water and new lands called deltas are formed.
4.14.1 Purification of water by alum (coagulation) : Alum 4.14.6 Clotting of blood : Blood consists of negatively
which yield Al 3 ions, is added to water to coagulate the charged colloidal particles (albuminoid substance). The
negatively charged clay particles. colloidal nature of blood explains why bleeding stops by
4.14.2 In rubber and tanning industry (coagulation and applying a ferric chloride solution to the wound. Actually
mutual coagulation) : Several industrial processes such as ferric chloride solution causes coagulation of blood to form
rubber plating, chrome tanning, dyeing, lubrication etc are a clot which stops further bleeding.
of colloidal nature. 4.14.7 Colloidal medicine : Argyrol and protargyrol are
colloidal solution of silver and are used as eye lotions. Colloidal
In rubber plating, the negatively charged particles of rubber
sulphur is used as disinfectant. Colloidal gold, calcium and
(latex) are made to deposit on the wires or handle of various
tools by means of electrophoresis. The article on which iron are used as tonics.
rubber is to be deposited is made anode. 4.14.8 Photographic plates : These are thin glass plates
coated with gelatin containing a fine suspension of silver
In tanning the positively charged colloidal particles of hides
bromide. The particles of silver bromide are colloidal in nature.
and leather are coagulated by impregnating them in
negatively charged tanning materials (present in the barks 5. EMULSIONS
of trees). Among the tanning agent chromium salts are most
“Emulsions are the colloidal solutions in which both the
commonly used for the coagulation of the hide material and
dispersed phase and the dispersion medium are liquids.”
the process is called chrome tanning.
A good example of an emulsion is milk in which fat globules
4.14.3 Artificial rains : It is possible to cause artificial rain
are dispersed in water. The size of the emulsified globules is
by throwing the electrified sand or silver iodide from an
generally of the order of 10–6m. Emulsion resemble lyophobic
aeroplane and thus coagulating the mist hanging in air.
sols in some properties.
SURFACE CHEMISTRY
along with the oil and water in the beginning. For Examples
: substances which can act as emulsifiers are soaps,
detergents, long chain sulphonic acid, lyophilic colloids like
gelatin, albumin, casein etc.
5.1 Types of Emulsion Different emulsifiers may act differently in the case of a
Depending upon the nature of the dispersed phase, the particular emulsion.
two components (oil and water) tend to separate out. To (e.g. KCl) to the emulsion. If this makes the emulsion
obtain a stable emulsion, a suitable stabilizing substance is electrically conducting , then water is the dispersion medium.
generally added. The stabilizing substance is called If water is not the dispersed phase.
5.5.2 These are coagulated by the addition of electrolytes 5.6.1 Concentration of ores in metallurgy
containing polyvalent metal ions indicating the negative 5.6.2 In medicine (Emulsion water-in-oil type)
charge on the globules.
5.6.3 Cleansing action of soaps.
5.5.3 The size of the dispersed particles in emulsions in larger
5.6.4 Milk, which is an important constituent of our diet an
than those in the sols. It ranges from 1000 Å to 10,000 Å.
emulsion of fat in water.
However, the size is smaller than the particles in suspensioins.
5.6.5 Digestion of fats in intestine is through emulsification.
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