Surface Chemistry and Colloidal state

Adsorption:
Due to unbalanced attraction forces, accumulation of molecular species at the surface rather than in the
bulk of a solid or liquid is termed as adsorption. The molecular species accumulates at the surface is termed
as adsorbate and the material on the surface of which the adsorption takes place is called adsorbent, e.g..
(i) O2, H2, Cl2, NB3 gases are adsorbed on the surface of charcoal.
(ii) (ii) Silica gels adsorb water molecules from air.
Charcoal, silica gel, metals such as Ni, Cu, Ag, Pt and colloids are some adsorbents
Desorption:
It is a process of removing an adsorbed substance from a surface on which it is adsorbed, is known as
desorption.
Absorption:
It involves the uniform distribution of molecular species throughout the bulk.
Sorption:
It is a process in which both adsorption and absorption take place simultaneously, the term sorption is
simply used.
Positive and Negative Adsorption
When the concentration of the adsorbate is more on the surface of the adsorbent than in the bulk, it is called
positive adsorption. On the other hand, if the concentration of the adsorbate is less relative to its
concentration in the bulk, it is called negative adsorption, e.g., when a dilute solution of KCl is shaken with
blood charcoal, it shows negative adsorption.

Factors Affecting Adsorption

(a) Nature of adsorbent: Same gas may be adsorbed to different extents on different adsorbent.
(b) Surface area of the adsorbent: Greater the surface area, greater is the extent of adsorption.
(c) Nature of the gas being adsorbed: Greater is the critical temperature of a gas, greater is the van der
Waals’ forces of attraction and thus, greater is the adsorption.
(d) Temperature: Adsorption is an exothermic process involving the equilibrium:
Gas (adsorbate) + Solid (adsorbent) ⇔ Gas adsorbed on solid + Heat
Applying Le-Chatelier principle, increase of temperature decreases the adsorption and viceversa.
Adsorption Isotherms
The curve between extent of adsorption and pressure at constant temperature is known as
adsorption isotherm. The rate constant for the desorption from the surface of solid follows Arrhenius type
relation and given as
kdesorption  Ae  Ea RT

The reciprocal of rate constant of desorption is known as life time (  ) of the adsorbate molecule on the
surface of solid.
   0e E a RT

1
where  0 is known as the pre-exponential factor and Ea is the desorption activation energy of the adsorbate.

The plot of T versus P for a given amount of adsorption is called adsorption isostere.
(e) Pressure Adsorption increases with pressure at constant temperature. The effect is large if temperature
is kept constant at low value.
(f) Activation of the solid adsorbent Activation means increasing the adsorbing power of the solid
adsorbent. This can be done by subdividing the solid adsorbent or by removing the gases already adsorbed
by passing superheated steam.

Freundlich Adsorption Isotherm

On the basis of experimental studies in 1909 Freundlich proposed an empirical relation between
the amounts of the gas adsorbed per unit mass of the adsorbent and the pressure.
x
 kp1 n ..................................................  4 
m
Taking logarithm of equation (4)
x 1
ln Slope = n
m
x 1
ln  ln k  ln p1 n
m n
Log k

ln P

 This equation is applicable to the adsorption of gases on solids. In the adsorption of solution on solids
the pressure in equation (4) can be replaced by concentration (c).
 The Freundlich adsorption isotherm explains the behavior of adsorption in approximate manner.
 The factor 1/n can have values between 0 and 1.
 At very low pressure n = 1, so
x
P
m
 At high pressure n = 0, so x/m remains almost constant
 At intermediate pressure the value of n lies from 0 to 1. so

2
 x 1
P n ……………………………………………….. (5)
m

Example: Among the following figures

(II) (III)
(I)
Mass adsorbe

Mass adsorbe

P P
Mass adsorbe
P
The variation of mass adsorbed with pressure for monolayer and multilayer are respectively are
(A) (I) and (III) (B) (I) and (II) (C) (III) and (I) (D) (II) and (I)
Ans: (B)
Example: One gram of charcoal adsorbs 100 mL of 0.5Macetic acid to form a monolayer and thereby the
molarity of acetic acid is reduced to 0.49 M. Calculate the surface area of the charcoal adsorbed by each
molecule of acetic acid. Surface area of charcoal is 3.01 x 102 m2/gm.
Solution.
initial moles of acetic acid = 0.5 x 0.1 = 0.05
moles of acetic acid left = 0.49 x 0.1 = 0.049
moles of acetic acid adsorbed = 0.05 – 0.049 = 0.001
molecules of acetic acid adsorbed = 0.001 x 6.023 x 1023 = 6.023 x 1020
3.01102
Area occupied by single molecule   5  1019 m 2
6.023 10 20

x
Example: A graph of log vs log P is plotted as shown below.
m

x 450
log
m
0.3

log P
x
What will be the value of when pressure is 0.4 atm?
m

3
Solution:
x 1
ln  ln K  ln P
m n
x 1
log  log K  log P
m n
From the figure
1
log K  0.3 and 1
n

x
log  0.3  log 0.4  0.698
m
Langmuir Adsorption Isotherm
The freundlich adsorption isotherm is valid over a certain range of pressure. To solve this
difficulty langmuir studied
i) All adsorption sites on the surface of the adsorbent are equivalent and the ability of a particle
to bind itself to a particular site is quite independent of the presence of other sites wether
occupied or not.
ii) The adsorbed layer on the solid adsorbent is assumed to be unimolecular in thickness.
iii) The process of adsorption is a dynamic process which involves condensation and evaporation.
iv) The rate of condensation of a gas is proportional to the uncovered surface of the solid
adsorbent while that of evaporation to its covered surface.
Let n molecules of the gas striking at one square cm of the surface of solid per second at
a pressure P. Let at any instant of time the fraction of the molecule condensing on the surface of
solid is x and the surface covered by the adsorbate molecule is  sq. cm.
The rate of condensation of gaseous molecule on the surface  k1 1    P
The rate of evaporation of gaseous molecule from the surface  k2
At adsorption equilibrium
k2  k1 1    P
P  k1

k2  Pk1
k1
P
k2

k
1 P  1
k2
P K
 ..............................(6
1 P  K
According to Lengmuir the degree of adsorption is directly propositional to  , so

4
 x

m
x P  kK PK '
 k   .......(7
m 1  P  K 1  PK P
Equation (7) can be represented as x/m
P 1 K 
 '   '  P.......(8
x m K K 
P

This equation (8) is called Langmuir’s adsorption isotherm.

 At low very pressure 1  KP , hence
x
 K ' P....................................... 9 
m
Thus at low pressure the amount of the gas adsorbed per unit quantity of adsorbent is directly
proportional to the pressure.
 At high pressure 1  KP hence
x K'
  constant....................................... 10 
m K
This equation shows that at high pressure, the amount of adsorbed gas is independent of pressure.
 At moderate pressure
x 1
 KP n the value of 1/n lies between 0 and 1.
m
Applications of Adsorption
1. For production of high vacuum.
2. Gas masks containing activated charcoal is used for breathing in coalmines. They adsorb
poisonous gases. ` Z
3. Silica and aluminium gels are used as adsorbents for controlling humidity.
4. Removal of colouring matter from solutions.
5. It is used in heterogeneous catalysis.
6. In separation of inert gas.
7. As adsorption indicators.
8. In chromatographic analysis.
9. Qualitative analysis, e.g., lake test for Al3+.

Colloidal state
Colloids are the substance whose aqueous solution passes through the parchment membrane. On
the basis of the size of the particles substance are divided into three types.
True Solutions Colloidal solutions Suspensions
1. Particle size is in the 1. Particle size is in the 1. Particle size is greater than
range of 1 -10 A0 range of 10 -1000 A0 1000 A0
2. Diffuse readily through 2. Diffuse slowly through 2. Generally do not diffuse.
parchment membrane. parchment membrane. 3. Do not scatter light.
3. Do not scatter light. 3. The particles scatter light.
The colloidal solution contains two phases called dispersion medium and dispersed phase.
Depending upon the nature of dispersion medium and dispersed phase the colloidal systems are dividing in
to the following types.

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 Dispersed phase Dispersion medium Type of colloid Example
Solid Solid Solid Sol Coloured glasses, Pigmented plastics
Solid Liquid Sol Paints, tooth paste, metallic dispersion
Solid Gas Solid aerosol Smoke, dust
Liquid Gas Aerosol Fog, Mist, Cloud
Liquid Solid Gel Opal, Pearls, Cheese, Jellies
Liquid Liquid Emulsion Milk, Hair, Cream
Gas Liquid Foam Soap, Lather, Froth, Whipped cream
Gas Solid Solid sol Foam rubber, Pumice stone
Lyophilic and Lyophobic Colloids
Colloidal solution in which the dispersed phase has high affinity for the dispersion medium is
called lyophilic colloids (solvent loving) and the colloids in which the dispersed phase has small affinity for
solvent is called lyophobi colloids).

Lyophilic Sol Lyophobic Sol

Relatively stable as strong force of interaction
Less stable as weak force of interaction exists between
exists between dispersed phase and dispersion
dispersed phase and dispersion medium.
medium
They are self stabilized They required an electrolyte for their stabilization
Can be prepared directly by mixing dispersed Cannot be prepared directly by mixing dispersed phase and
phase with dispersion medium. dispersion medium.
No need of stabilizers during preparation. Additional stabilisers are required during preparation.
They are reversible in nature. They are irreversible in nature.
These are usually formed by organic These are usually formed by inorganic materials like
substances like starch, gum, proteins etc. metals and their oxides, sulphides etc.
They are highly viscous and have higher
They have nearly the same viscosity as that of the medium.
viscosity than that of the medium.
They are highly hydrated. They are not much hydrated.
Particles cannot be detected even under an
Particles can be detected under an ultramicroscope.
ultramicroscope.
Charge on the lyophilic sol can be postive, Charge on the lyophobic sol can be postive or negative.
negative or netural. As2S3 sol is -ve and Fe(OH)3 sol is +ve in nature.
Depending on the charge, their particles Depending on the charge, their particles migrate only in
migrate to either direction of an electric field. one direction of an electric field.
Surface tension is usually lower than that of the Surface tension is nearly the same as that of the dispersion
dispersion medium. medium.
Starch, gum and egg albumin are the examples Fe(OH)3, As2S3

Preparation of lyophobic sols

Dispersion methods
In this method the bigger particles are break down into smaller particles. The dispersion methods
involved the following techniques.
i) Mechanical Dispersion:
In this method the coarse particles of dispersed phase in presence of dispersion medium
are grinded into smaller colloidal size particles in a colloidal mill. Rubber, ink, paints and
varnishes are prepared by this method.
ii) Electrical Dispersion (Bredig’s arc method)

6
 This method is used to prepare the colloidal solution of metals. An electric arc is struck
between two metallic rods kept in dispersion medium. Svedberg has shown that the
electrical methods are suitable not only for preparing the hydro sols of metals like gold,
silver, platinum, copper etc but also for sols of strongly electropositive metals in non
aqueous medium.
iii) Peptization
This process involves the conversion the fresh precipitate into colloidal solution by
dissolving the precipitate into a suitable solvent. The electrolyte used to prepare colloidal
solution is called peptizing agent.
For example:
 the colloidal solution of Fe(OH)3 is prepared by dissolving the precipitate in a small
amount of FeCl3.
 Colloidal solution of AgCl is prepared by adding fresh precipitate into HCl solution.

iv) Dispersion by ultrasonic waves

The substance like oils, sulphur, graphite, sulphides and oxides of metals can be
dispersed very easily by sound waves of very high frequency of the order of 20000
cycles/sec.
Condensation methods
In this method the atoms or molecules of the substance are condensed together forms colloidal
particles.
Pc
Initial rate of condensation (r) ............................................... 1
k
Rc
where Pc is condensation pressure, Rc is condensation resistance and k is a constant.
According to Von Weimarn, the normal solubility (s) of a substance separating out from the solution may
be regarded as a measure of condensation resistance and the difference between the total concentration (c)
and normal solubility may be equal to the condensation pressure. Thus we have

cs
rk ........................................  2 
s
The condensation can be brought by the following methods
i) Oxidation
The colloidal solutions of some non-metals are prepared by this method. For example the
colloidal solution of sulphur is prepared by passing H2S gas through bromine water or dil
HNO3 solution.
H2S + Br2  2HBr + S
H2S + 2HNO3  2H2O + 2NO2 + S
ii) Reduction
Colloidal solutions of some metal are obtained by reduction of their salts. For example
gold sol can be prepared by reduction of Au3+ with tannic acid, formaldehyde, hydrogen
peroxide, phosphorus, hydrazine etc.
2AuCl3 + 3 HCHO + 3H2O  2Au + 3 HCOOH + 6HCl
4AuCl3 + 3NH2NH2  4Au + 3 N2 + 12HCl
iii) Double Decomposition
This method is often used to prepare various colloidal solutions. A sol of arsenious
sulphide is prepared by passing H2S gas through a dilute solution of arsenious oxide and
removing the excess of H2S gas by boiling.
As2O3 + 3H2S  As2S3 + 3H2O
iv) Hydrolysis
The colloidal solution of Fe(OH)3 is prepared by hydrolysis of FeCl3 solution.
FeCl3 + 3H2O  Fe(OH)3 + 3HCl

7
 Boiling promotes the reaction because HCl formed is removed along with water vapors
from the system. In this reaction iron oxychloride FeOCl, formed as a result of
incomplete hydrolysis can acts as stabilizer.
Properties of Colloids
Heterogeneous nature:
Unlike true solutions the colloidal solutions are heterogeneous in nature. Experiments
like dialysis, ultrafiltration, ultracentrifugation etc. indicates the heterogeneous nature of
colloidal solutions.
Concentration and density of sol
Most of the sols are stable in dilute solutions, but the colloidal particle is converted in to
suspension when volume of the dispersion medium decreases. According to Cholodny
the density of sols increase linearly with the concentration. The density of the sol is
related with concentration by the following equation
0  
s    C ...................................... 1

where  s ,  0 &  are the densities of sol, solvent and dispersed substances respectively,
and C is the concentration of dispersed substance in gram/ml.
Colour
The colour of the colloidal solutions depends on the size and shape of the colloidal particles. The
colour of the colloidal solutions is also depends on wavelength of light, method of preparation, the way by
which an observer receives the light etc. For example dilute milk gives a bluish tinge in reflected light and
reddish tings in transmitted light.
Tyndal effect
When a beam of converging rays falls in colloidal solution, scattering of light by sol particle in all
the directions, gives rise to a bright glowing cone when looked at it sideways. This effect is known as
Tyndal effect. The tyndal effect is due to scattering of light by the colloidal particles. The colloidal particles
first absorb light and then a part of the absorbed light and then a part of the absorbed light is scattered from
the surface of the colloidal particles. Maximum scattered intensity being in a plane of incident light, the
path of the light becomes visible when seen from that direction. The scattering of light increase with
increasing the size of dispersed phase as well as difference in refractive indices of dispersed phase and
dispersion medium. If the colloidal particles are assumed to be small and exhibit no absorption of their
own, then it may be observed that
(i) The intensity of the scattered light is highest in the direction parallel to the incident beam and
smallest in the direction perpendicular to the incident beam.
(ii) The scattered light in the perpendicular direction is completely polarized with its electric
vector perpendicular to the direction of the incident beam. The polarization is minimum in the
direction of incident light.
(iii) The intensity of the scattered light increase as the wavelength of the light decrease, and hence
the tyndal beam assumes a blue colour, imparting the complimentary yellow colour to the
transmitted light.
The tyndal effect is observed when
 The diameter of the dispersed particle is not much smaller than the wavelength of the light
used.
 The refractive indices of the dispersed phase and dispersion medium differ greatly in
magnitude

Brownian motion
The zig-zag motion of colloidal particle is known as Brownian motion. This type of motion
originates from the molecular impacts from the medium molecules on all side of the particle. The
Brownian movement becomes less and less prominent as the size of colloidal particle increase or the
viscosity of the medium increases. The mean Brownian displacement ( x ) of a particle from its
original position along a given axis after a time t is given as
( x )  2dt .........................................  2 

8
 RT
where d is diffusion coefficient and equals to . Therefore
6 rN A

RT
(x )  t ..........................................  3
3 rN A
where  is the coefficient of viscosity, r is the radius of the particle and N A is the Avogadro’s number.
The Brownian movement opposes the force of gravity and does not allow the colloidal particle to settle
down. Thus it is responsible for the stability of the colloidal solutions.
Origin of Charge on Colloidal Particles
The origin of charge on colloidal particles depends on the nature of sol. The charge on the
colloidal particles is due to one or more of the following reasons:
 Frictional electrification caused by the mutual rubbing of the colloidal particles with the particles
of dispersion medium.
 Electron capture by particles from air and during electro-dispersion in Bredig’s arc method.
 Dissociation of molecules followed by aggregation of ions. For example the colloid particles of
soaps dissociates in solution to furnish the ions having the long chain (hydrophobic part) of carbon
atoms. These anions aggregate to form a micelle of colloidal dimension and have negative charge.
 Due to the presence of acidic and basic group: A protein molecule has a carboxylic and amino
group. The particles of protein in colloids are either positively charged or negatively charged
depending upon the pH of solution.
 Due to select adsorption
According to this theory the charge on colloidal particle is due to the adsorption of ion from
dispersion medium onto the surface of the particle, therefore the charge on the particle is similar to
the charge on adsorbed ions. The adsorbed ion should be common to its own lattice. For example
the colloidal solution of Fe(OH)3 in FeCl3 is positively charged because Fe3+ ions are adsorbs on
the surface of the particle. Similarly the colloidal particle of As2S3 adsorbs S2- ions hence the
colloidal of particle As2S3 are negatively charged.

Cl - Cl - H+ H +
Cl - Cl - H+ H+
-
3+ Cl
2-
3+ +
2- S S 2- H+
Cl Fe3+ Fe Fe
- H
S
H + S 2- S 2- H +
Fe(OH) Fe 3+
Cl -
As 2S3
Cl - Fe3+ S 2- H +
Fe3+ H+ S 2-
Cl - Fe 3+
Cl - S 2- H +
Fe3+ H+ S 2-
-
Cl Cl - H+ H+
Cl - H+ H+

Colloidal Solution of Fe(OH)3 Colloidal Solution of As2S3

Electrical Double Layer Theory
 The dispersion medium forms electrical double layer on the surface of colloidal particle.
 The first layer is called fixed layer and second layer is called diffused layer.
 The second layer contains the both cations and anions.
- + - + - + - + -+ - + - - -- + -+ - + -
+
+ - + - + - + - + - + - +- } Diffused layer { +- +- + +- + -
+ - + - + - +-
+++++++++++ +++++++ } Fixed layer { ------------------
Solid Solid

Positively charged colloid Negatively charged colloid

 The ions which are preferentially adsorbed by colloidal particle are retained in the fixed layer.
 The charge on the colloidal particles is due to the adsorption of ions of first layers.
 The opposite charge of fixed layer and diffused layer results in a difference in potential between
these layers called zeta potential.

9
 4 u
 , where  = coefficient of viscosity, u = velocity of particles and D = dielectric
D
constant of medium
 The presence of charge on colloidal particles of lyophobic sol provides the stability of the sol.
Coagulation of Colloidal Solution
A small amount of electrolyte essential for the stability of sols, and large amounts of electrolytes
can cause the coagulation. This is due to the fact that the addition of oppositely charged electrolyte
destroyed the charge on colloidal particle, hence colloidal particle gets coagulated. According to Hardy and
Schulze
 Coagulation is brought about by ions having opposite charge to that of the sol. A negatively
charged ions cause coagulation of the positively charged sols and positive ions cause coagulation
of negatively charged sols.
 The efficiency of coagulative ion varies directly as the square of the valency of the ion.
 The minimum concentration of an electrolyte in millimoles required to cause coagulation or
flocculation of 1L sol in 2hrs is called its flocculation value.
 The flocculation power is the reciprocal of coagulation value.
1
 Usually, the flocculation value of the ions is quantitatively described as where x is the
 x
6

valency of the coagulating ion.

The following factor affects the coagulation of sol.
1. Nature of sol
2. Nature of charge on sol particle.
3. Valency of the precipitating ions.
4. The mode of defining coagulation.
5. Rise in temperature favors coagulation.
6. Time allowed for coagulating
7. The ratio of surface to mass of dispersed phase.

Protection of Colloids
The action of hydrophilic colloids to prevent the precipitation of the hydrophobic colloids by the addition
on an electrolyte is called protection and the hydrophilic colloid is called protective colloid. The particles of
protective colloids gets adsorbs on the surface of hydrophobic colloids in the form of loops wherein water
gets trapped. These loops prevent the particles towards coagulation. According to Zsigmondy the protective
power of colloid depends on the nature of substance, and can be expressed in terms in Gold number. The
gold number may be defined as
“The amount of protective colloid in milligram necessary for the protection of 10 c.c of a gold solution by
the addition of 1 c.c. of 10% NaCl solution”
The protective power of colloid increases with increasing gold number.
Protective Colloid Gold Number
Gelatin 0.005 to o.1
Haemoglobin 0.03 to 0.07
Gum Arabic 1.5 to 25
Egg Albumin 0.025 to 25
Starch 15 to 25
Saponin 0.015 to 115
The protective power can also be measured in terms of Congo Robin number which is defined as
“ the amount of protective colloid in milligram which prevents colour change in 100 ml of 0.01% cango
robin dye solution to which 0.16 gm equivalent of KCl is added when observed after 10-15 minutes.
Associated Colloids
 Association colloids are formed by the association of long chain organic compounds, such as fatty
acids, quaternary ammonium salts etc. These are also known as surface active agents.

10
 A surface active substance has hydrophilic and hydrophobic parts in its structure. When dissolved in
water their solution contains isolated molecules upto a certain concentration. However they grow in
weight and size above a certain concentration and enter into the colloidal region.
 For example in case of soap the molecules aggregate by themselves when the concentration is above a
certain concentration, this aggregation of molecules forms a particle of colloidal dimension is called
ionic micelles.
 The formation of micelles take place only above a particular concentration called critical micelles
concentration (CMC).

+
O Na
Sodium laureate Hydrophilic part
(Soap)

 The surface activity increases with increasing the length of hydrophobic chain.
 It is a spontaneous process, so
G  H  T S  0
H  ve, S  ve
the main contribution to the G is S as the change in entropy is almost insignificant.
In general the free energy change of micelles formation is represented as
G  RT ln  CMC 
 At low concentration the surfactant ions pass into the surface layer at the interface of the surfactant
with the other phase hence free energy of the system decrease. As the surface layer gets saturated
further increase in the concentration, the system expels the hydrophobic chains from the water in to the
liquid “pseudophase” –micelles, and separates it from the water by the hydrophilic shell of the polar
group. This is called self-adsorption and cause gain in energy (about 1,08kT or 2600J per CH 2) group.
 The gain in energy increases with increasing length of carbon chain, so the CMC decreases with
increasing the length of carbon chain of surfactant molecule.
 Increase in temperature increases the CMC.
 The minimum temperature at which the CMC achieved is called Craft temperature. Below the Craft
temperature the solubility of surfactant is not enough to form micelles. Craft temperature increases
with increase in the number of carbon atoms in hydrophobic part.
 CMC of ionic micelles decreases on addition of strong electrolytes because the screening action of
charged ions reduces the repulsion between charged groups at the surface of the micelles.
 Physico-chemical properties of surfactants solution changes sharply in the CMC range.
CMC
Turbidity
Relative unit measured

Osmotic pressure

Surface tension
Molar electrolytic
conductance

Concentration

11
Macromolecules
The molecules with large dimension are called macromolecules. The suspension of these
molecules in a suitable medium behaves naturally as a colloid. Some of the macromolecules dissolve in
water giving true solution. But the large size and shape of these molecule cause serious deviation from
normal solutions. The solutions of macromolecules behave like lyophilic colloids.
The Number Average Molecular Weight

Mn 
n1M 1  n2 M 2  ...........

n M
i i

n1  n2  .............. n i

where n1 , n2 ……are number of moles and M 1 , M 2 ……..are molecular weight of the substance.
The Weight Average Molecular Weight
n M 2  n2 M 22  ...........  ni M i
2

Mw  1 1 
n1M 1  n2 M 2  ..............  ni M i
where n is number of moles and M is molecular weight. The polymer solutions show considerable
deviation from Raoult’s law. Such solutions show negligible, elevation in boiling point and depression in
freezing point. The osmotic pressure of these solutions can be easily calculated therefore molecular weight
of polymers can be calculated by osmotic pressure.

12