Chapter 6

SURFACE CHEMISTRY
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or
dissolved solid to a surface. This process creates a film of the adsorbate on the
surface of the adsorbent. Adsorption is a surface phenomenon.

adsorbent adsorbent
The extent of surface coverage is normally expressed as the
fractional coverage, θ:
θ = number of adsorption sites occupied
number of adsorption sites available

• The fractional coverage is often expressed in terms of the

volume of adsorbate adsorbed by θ = V/V∞, where V is the
volume of adsorbate corresponding to complete monolayer
coverage.

• The rate of adsorption, dθ/dt, is the rate of change of surface

coverage, and can be determined by observing the change of
fractional coverage with time.
Physisorption and chemisorption
Molecules and atoms can attach to surfaces in two ways:

1. Physisorption (physical adsorption)

• In physisorption the molecules attached to the surface by van der Waals
interaction.
• The enthalpy of physisorption can be measured by monitoring the rise in
temperature of a sample of known heat capacity, ≈20 kJmol-1.
2.Chemisorption (chemical adsorption)
• In chemisorption the molecules (or atoms) stick to the surface by
forming a chemical bond (usually covalent bond), and tend to find
sites that maximize their coordination number with the substrate.
• The enthalpy of chemisorption is >>> physisorption, ≈ of 200 kJ mol-1.
• A spontaneous process requires ΔG<0 i.e ΔG = ΔH - TΔS <0.
• The principal test for distinguishing chemisorption from physisorption
used to be the enthalpy of adsorption.
• Values less negative than -25 kJmol-1 were taken to signify
physisorption, and values more negative than about -40 kJmol-1 were
taken to signify chemisorption.
Adsorption isotherms
The fractional coverage of the surface depends on the pressure of the
overlying gas. The variation of θ with pressure at a constant temperature is
called the adsorption isotherm.

(a) Langmuir isotherm

Based on 3 assumptions:
1. Adsorption cannot proceed beyond monolayer coverage.
2. All sites are equivalent and the surface is uniform (i.e, the surface is
perfect)
3. The ability of a molecule to adsorb at a given site is independent of
the occupation of neighbouring sites.

The dynamic equilibrium is:

ka
A(g) + M(surface) ↔ AM(surface)
kd
 ka = rate constants for adsorption
kd = rate constant for desorption.
the rate of change of surface coverage due to adsorption is proportional to the
partial pressure of P and the number of vacant sites N(1- θ), where N is the total
number of sites:
dθ/dt = kaPN(1-θ)

The rate of change of θ due to desorption is proportional to the number of

adsorbed species, Nθ :

dθ/dt = -kdNθ

At equilibrium there is no net change (that is, the sum of these two rates is
zero), and solving for θ gives the Langmuir isotherm:

θ = KP K = ka
1 + KP kd
 : 
ADSORPTION ISOTHERM
(gas adsorbed on solid surfaces)
Langmuir Isotherm BET
Monolayer coverage
A(g) + S ↔ A(g)S
where A is a gas molecule
and S is an adsorption site.
LANGMUIR

BET isotherm:
Multilayers may forms when
some molecules are adsorbed on
already adsorbed.
A(g) + S ⇌ AS,
A(g) + AS ⇌ A2S,
adsorption process of N2(g) on adsorbent A(g) + A2S ⇌ A3S and so on.
(aerogel)
Langmuir isotherm (monolayer formation)
Shapes of Langmuir isotherms with or
without dissociation:
-the maximum volume of gas adsorbed
reach maximum when the equilibrium
BET
establish in the gas phase and the
corresponding adsorbed species shown by
the levelling off in the graph
-The fractional maximum is obtained at very
high pressure when the gas is forced on to
every available site of the surface.
LANGMUIR
-Curve is dependent to temperature

BET isotherm (multilayer formation)

-shapes of BET isotherms rise indefinitely
as pressure increased because there is no
limit to the amount of material
-adsorbed layer may act as a substrate for
further adsorption therefore the curve does
not come to equilibrium (levelling off),
instead it may rise indefinitely.
-similar as Langmuir isotherm, BET
isotherm dependent on the temperature.
For adsorption with dissociation, the rate of adsorption is proportional to the
pressure and to the probability that both atoms will find sites, which is
proportional to the square of the number of vacant sites,

dθ = kdP (N(1-θ))2
dt

The rate of desorption is proportional to the frequency of encounters of atoms

on the surface, and is therefore second-order in the number of atoms present:

dθ = -kd(Nθ)2
dt
The condition for no net change leads to the isotherm

θ = (KP)1/2
1 + (KP)1/2
Example:
The data given below are for the adsorption of CO on charcoal at 273 K. Confirm
that they fit the Langmuir isotherm,and find the constant K and the volume
corresponding to complete coverage. In each case V has been corrected to 1.00
atm.

p/Torr 100 200 300 400 500 600 700

V/cm3 10.2 18.6 25.5 31.5 36.9 41.6 46.1

Answer:
From eq, Kpθ + θ = Kp

When θ = V/V∞ where V∞ is the volume corresponding to complete coverage, this

expression can be arranged into
P/V = P/V∞ + 1/KV∞

Hence a plot of p/V against P should give a straight line of slope 1/V∞ and intercept
1/K∞.

Data for the plot:

p/Torr 100 200 300 400 500 600 700
(p/torr)/(V/cm3) 9.80 10.8 11.8 12.7 13.6 14.4 15.2
 1 2
y = +0.00900x +9.01, max dev:0.114, r =0.998

15.0

(p/torr)/(V/cm3) 12.5

10.0

7.5

0 200 400 600 800

p/torr

From the graph, the slope = 0.009, so V∞ = 1÷0.009 = 111 cm3. The
intercept at p = 0 is 9.01, therefore:

K= 1 = 1.00 x 10 -3 torr-1
(111 cm3) x (9.01 torr cm-3)
Question:
Repeat the calculation for the following data:

p/torr 100 200 300 400 500 600 700

V/cm3 10.3 19.3 27.3 34.1 40.0 45.5 48.0

Answer: 128 cm3; 8.89 x 10-4 Torr-1

(b) BET isotherm

• If the initial adsorbed layer can act as a substrate for further adsorption.
Then, instead of the isotherm levelling off to some saturated value at high
pressures, it can be expected to rise indefinitely.

V = cz ;z=P
Vmon (1-z) {1-(1-c)z} P*

• p* = vapour pressure above a layer of adsorbate.

• Vmon = volume corresponding to monolayer coverage.
• c = a constant which is large when the enthalpy of desorption from a monolayer
c = e (ΔdesHθ - ΔvapHθ)/RT

When c >> 1, the BET isotherm takes the simpler form

V = 1
Vmon 1-z
Example 2
The data below relate the adsorption of N2 on rutile (TiO2) at 75 K. Confirm that
they fit a BET isotherm in the range of pressures reported, and determine Vmon
and c.

p/torr 1.2 14.0 45.8 87.5 127.7 164.4 204.7

V/mm3 601 720 822 935 1046 1146 1254

At 75 K, p*=570 Torr. The volumes have been corrected to 1.00 atm and 273 K
and refer to 1.00 g of substrate.

Answer:
Using BET eq, which can be reorganized to z = 1 + (c-1) z
(1-z)V cVmon cVmon

y = C + mx

(c-1)/cVmon can be obtained from the slope of a plot of the expression on the
left against z and cVmon can be found from the intercept at z=0. The results can
then be combined to give c and Vmon.
 Data:
p/torr 1.2 14.0 45.8 87.5 127.7 164.4 204.7
10-3z 2.11 24.6 80.4 154 224 288 359
10-4z/(1-Z)(v/mm3) 0.035 0.35 1.06 1.95 2.76 3.53 4.47
5

y=1.23x10-2x + 0.0406
z=p/p* ; p* =570
10-4z/{(1-z)(V/mm3)}
4

z= 1.2 ÷ 570=0.0021
3
z = 0.0021
Slope = 2 1-z(V) (1-0.0021)(V)
(y2-y1) / (x2-x1)
= 0.0021
1 0.9979(601)

0 = 3.5x10-6 or
0 100 200 300 400
0.035 x 10-4
10 z
-3

The intercept = 0.0406, therefore 1/cVmon = 4.06 x 10-6 mm-3

the slope of the line is 1.23 x 10-2, so
c-1/cVmon = (1.23 x 10-2) x 103 x 10-4 mm-3 = 1.23 x 10-3 mm-3

Solving the equation, we get c=303 and Vmon= 814 mm3

Question 2:

Repeat the calculation for the following data:

p/torr 1.2 14 45.8 87.5 127.7 164.4 204.7

V/cm3 235 559 649 719 790 860 950

Answer: 370, 615 cm3

The rates of surface processes

• As the molecule approaches the surface its energy falls as it

becomes physisorbed into the precursor state for chemisorption.
Dissociation into fragments often takes place as the molecules
moves into its chemisorb state.

• Chemisorption is not an activated process and can be expected to

be rapid. Many gas adsorptions on clean metals appear to be non-
activated.

• Chemisorption can be fast if the activation energy is small or zero,

but it may be slow if the activation energy is large.

• Physisorption is usually fast, but it can appear to be slow if

adsorption is taking place on a porous medium.
Type of isotherms
Type of isotherms is useful for characterisation of porous materials. There are 6
types of isotherms useful for this purpose, as shown below.

The 6 type of absorption isotherms

COLLOID

True solution: One phase system. The solute particles consists of individual
molecules or ions; eg: sugar or salt dissolve in water.

Suspension: particles contain more than one molecules and are large enough to
be seen by the eye or at least under a microscope.

Colloidal disperson: two-phase system-definite surface of separation between

particles and disperse medium. Particles may contain more than one molecules
but are not large enough to be seen in a microscope, dimension = 5-200 nm);
e.g micromolecules such as starch and protein. Solution of these substances
exhibit colloidal behavior, and although they are single molecules, they are
classified as colloidalmsystem.

Disperse phase is refer to the particles that are present in the dispersion
medium. Both the disperse phase and the dispersion medium may be solid,
liquid or gaseous.
Colloidal dispersion
Heterogenous system with 2 distinct
phases. Solutes have definite surfaces or
interfaces which are sufficiently large
and separate from the solvent
Physical properties determined by the
characteristic surface properties;
adsorption and electric double layer on
the interfaces of the colloidal particles
Example:starch solution and milk
Particle: colloidal particles
Consists of many
atoms/ions/molecules/single giant
molecules
Size: 1 to 100 nm
scatter light-tyndal effect
Can be filtered from the solvent by
membrane filter
Cannot be filtered by ordinary filtration
True solution
Homogeneous system with only one
phase. No true separation between
particles of solute and solvent.
Physical properties:chemical bonds and
the electronegativities of the atoms
Example: Sugar or salt on water
Particle:Solute particles
Individual molecular or ions
Size: less than 1 nm
No tyndall effect
Cannot be filtered
Cannot be filtered by ordinary filtration
 Disperse phase – refers to the colloidal particles present in the dispersion
medium. The disperse phase and medium maybe solid, liquid and gaseous.
Gases are always completely miscible, we cannot have gas-in-gas colloidal
dispersion. Possible combinations are listed in the following table:

Dispersion Disperse phase Name of system examples

medium
Gas Liquid Aerosol fog., mist, cloud
Gas Solid Aerosol Smoke
Liquid Gas Foam Whipped cream
Liquid Liquid Emulsion Milk, mayonnaise
Liquid Solid Sol Gold in water
Solid Liquid Gel Jelly
Solid Solid Gel Ruby glass, gold in glass
solid gas Solid foam styrofoam
TYPES of SOLs
Colloidal disperson of solids and liquids (sols) can be divided into two types:

1.Lyophobic Sols
•is called hydrophobic sols (if the dispersion medium is water)
•Relatively unstable
•The addition of electrolyte to lyophobic Sols frequently causes coagulation
and precipitation
2. Lyophilic
•A liquid-loving sols
•Has strong affinity between the disperse phase and the molecules
comprising the dispersion medium
•Much more stable and behave much more like true solution

-terms lyophobic/lyophilic are used to describe the tendency of a surface or

functional group on the disperse phase to become wetted or solvated by a
dispersion medium.
Gels
Lyophilic sols may coagulate and form A semirigid mass that include the whole
liquid include in the sol. This is known as gel.

Two kind of gel : elastic (jellies, cornstarch puddings, jams) and nonelastic gels
(silica gel)

Difference :
1. Dehydration:
- elastic gel leads to formation of elastic solid from which the original sols can be
regenerated by addition of water. Dehydration of nonelastic gel leads to the
formation of glass powder.

2. Ability to take up water

-Elastic gel may take up water and swells– water is imbibed into the gel –
imbibation process.
-Nonelastic gels do not swell-the liquid enter the pores of the gel but it do not swell
because of wall is rigid, therefore the volume of the gel does not change.
 Classfication of sols/colloid

• Lyophilic sols (hydrophilic if solvent is

water) – solvent loving
eg: starch, milk, albumin, blood
plasma , gel, glue

• Lyophobic sols – solvent hating

eg: sulfur , gold , Fe(OH)3 , Al(OH)3

December 12, 2021 27

 PROPERTIES OF LYOPHILIC SOL

• Reversible sols
• Dispersed phase (particles) can attract the
molecules of dispersing medium
• High viscosity of dispersing medium
• Surface tension of dispersed phase is lower –
easier to form bubble

December 12, 2021 28

 Preparation of lyophilic sols
-easy to prepare
• prepared by stirring the solid with the
dispersing medium such as water
• Heating the mixture will disperse the solid
throughout the dispersing medium

December 12, 2021 29

 Examples: preparation of lyophilic sols

• Rubber sol – mixing latex in excess of petrol or

benzene

• Soap – heating of fatty acid such as octadecanoic

acid and NaOH in ethanol

• Starch, gel, gelatin- heating a mixture of solid and

water to form sol, when cooled it changes into gel.

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 Properties of lyophobic sol
(hydrophobic – if dispersing medium is water)
• Irreversible
• No attractive force between dispersed phase
and dispersing medium
• Viscosity is not different
• Surface tension of the dispersed phase and
dispersing medium are the same

December 12, 2021 31

 Preparation of lyophobic sols
(more difficult to prepare-need specific method)
a) Dispersion method
- mechanical dispersion
- peptization
- Bredig’s arc dispersion method

b) Condensation methods
- hydrolysis
- oxidation
- reduction

December 12, 2021 32

 Bredig's Arc Method
• an electric arc is struck between
electrodes of the metal immersed in
the dispersion medium.

• The intense heat produced by the

arc vaporizes the metal, which then
condenses to form particles of
colloidal size.

• By this method, sols of metals such

as gold, silver and platinum can be
prepared.

December 12, 2021 33

 Purification of Colloidal Sols
• The colloidal solutions prepared by various methods
usually contain electrolytes and other soluble
substances as impurities.

• this impurities may destabilize the sols. Impurities are

removed by : 
1) Dialysis 
2) Ultra-filtration 
3) Ultra-Centrifugation.

December 12, 2021 34

Purification of Colloidal Sols - dialysis
 Properties of Colloids/sols
• Optical properties
1. Tyndall effect
2. Brownian movement

• Electrical properties
1. Electrophoresis
2. Electro-osmosis

December 12, 2021 36

TYNDAL EFFECT - LIGHT SCATTERING BY COLLOIDAL PARTICLES

- colloidal particle scattered some of the light and the incident beam passed
through with weakened intensity
•The scattering is called Tyndall effect
•The path of the light through the medium, made visible as a result of
scattering is known as Tyndall beam

Example:
Sunbeam can be observed when light is scattered by fine dust particles

•Analysis of the scattering as a function of the angles provide valuable

information about the sizes and shapes of colloidal particles
•When these are singles macromolecules, the technique is therefore useful
in determining molar mass
The proportion of incident light that is scattered increases with the increase of
number and size of the particles.

The intensity of transmitted radiation is given by

I = Ioe-τI

Where τ is turbidity, Io = intensity of the incident radiation , I=the length of the light
path through the scattering medium.

For a spherical particle where (r<<<𝝀), the intensity of the radiation scattered
through an angle theta θ, is given by Raleigh equation:

Iθ = [Ksr6(1+cos2θ)]/𝝀 4 (Raleigh equation)

Ks=refractive index of the particle and medium
 Brownian movement
• Colloidal particles are too small to be visible.
• These particles can be only be seen under a high-
power microscope when a bean of light is passed
through the colloidal solution.
• The particles of colloidal solution move randomly
in dispersing medium and show themselves as
they were ‘alive’.
• Smaller particles move more rapidly without any
order or pattern.

December 12, 2021 39

Electrical property – Electrophoresis experiment
-to determine the charge on colloidal particles
-Electrical potential is applied across two platinum electrodes
dipping in a colloidal sols.
-vely charged particles move towards the cathode; +ve
particles under an applied electric potential is called
electrophoresis.
 Coagulation and Flocculation
Coagulation is the process by which a colloid precipitates out of
a solution.
Lyophilic sols
-are more stable
-show greater resistance to coagulation than lyophobic sols
because most of lyophilic sols are neutral.
- a large amount of electrolytes are required to coagulate these sols.
- this is due to the strong attraction between the disperse phase and
dispersing medium such as hydrogen bonds.

Lyophobic sols
-are stable due to repulsion between similarly charged particles.
-If this charge is removed by adding electrolytes, coagulation occurs.
-The particles come together to form larger masses, which settles under
the action of graviti.

December 12, 2021 41

 COAGULATION
• Definition
Destabilisation of colloid particles by the
addition of chemicals (coagulant)
• Applications
Industrial waste containing colloidal and
suspended solids (e.g. pulp and paper, textile)
 Flocculation
• is a process of forming aggregate of flocs to
form larger settleable particle. The process
can be described as follows:
 collision of small floc resulting in bigger size.
 Usually slow speed or gentle mixing is used so
as not to break the large flocs
 Polymer or large molecular weight compound
is added to enhance floc build up. Most of
them are proprietary chemicals.
Flocculation mechanism
 Coagulant - Reaction
• Some of the coagulants used include:
 Aluminium sulphate
 Ferric chloride
 Ferric sulphate
 Lime (not true coagulant)
 Polymer as coagulant aid eg cationic, anionic, non-ionic.
 PAC – new types

Al2(SO4)3.18H20+ 3Ca(HCO3) 2AI(OH)3+

3CaSO4+ 6C02 + 18H20
AI(OH)3 or Al2O3 ( form as floc is the key element causing
destabilisation of charge).
Effect of different cation/anion on coagulation proces:

The quantity of the electrolyte which is required to coagulate a definite

amount of a colloidal solution depends on the valency of the ion having a
charge opposite to that of the colloidal particles. This observation on Hardy
and Schulze are known as Hardy Schulze law.

Hardy Schulze law : the precepitating effect of an ion on a disperse

phase of opposite charge increase with the valency of the ion.

Therefore:
greater is the valency of the opposite charged ion of the elecrolyte being
added, the faster is the coagulation

Example: in the coagulation of negatively charged arsenous sulphide sol,

trivalent cations are far more effective than divalent cations which in turn are
more effective than monovalent cations. Similarly, in the coagulation of
positively charged ferric hydroxide sol, tetravalent anions are more effective
than trivalent anions which are more effective than divalent anions and more
effective than monovalent anions.
Coagulation value:
The minimum amount of an electrolyte that must be added to one liter of a
colloidal solution so as to bring about complete coagulation or flocculation is
called the coagulation or flocculation value of the electrolyte. Thus smaller is
the flocculation value of an electrolyte, greater is the coagulating or
precipitating power.

Example: coagulation of negatively charged colloids As2S3

Electrolyte NaCl MgCl2 BaCl2 AlCl3

Cation Na+ Mg2+ Ba2+ Al3+
Coagulation values 52 0.72 0.69 0.093

Example: coagulation of positively charged colloids Fe(OH)3

Electrolyte KBr K2SO4 K2C2O4

Cation Br- SO42- C2O42-

Coagulation values 138 0.210 0.238