3 - M - SC - (Chemistry) - 344 23 - Physical Chemistry II

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YTISREVINUALAGAPPA
APPAGALAUNIVERSITY
M.Sc. [Chemistry] elcyC drihT eht ni )46.3:APGC( CA[Accredited
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taC Graded
sa dedarasG Category–I
dna University by MHRD-UGC]
300 036 – IDUKIARA
KARAIKUDI
K – 630 003
344 23 NOITACUDE ECNATSIDDIRECTORATE
FO ETAROTCEOF
RIDDISTANCE EDUCATION
PHYSICAL CHEMISTRY - II
II - Semester
PHYSICAL CHEMISTRY – II
M.Sc. [Chemistry]
344 23
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TISREVINUALAGAPPA
APPAGALAUNIVERSITY
yC drihT eht ni )46.3:APGC( CA[Accredited
AN yb edarGwith
’+A’’A+’
htiwGrade
detidby
ercNAAC
taC Graded
M.Sc. [Chemistry]
KARAIKUDI
K – 630 003
NOITACUDE ECNATSIDDIRECTORATE
FO ETAROTCEOF
II - Semester
ALAGAPPA UNIVERSITY
[Accredited with ‘A+’ Grade by NAAC (CGPA:3.64) in the Third Cycle
and Graded as Category–I University by MHRD-UGC]
(A State University Established by the Government of Tamil Nadu)
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Directorate of Distance Education
M.Sc. [Chemistry]
II - Semester
344 23
Authors:
Late K K Sharma, Department of Chemistry, Zakir Husain College, University of Delhi
L K Sharma, Former Associate Professor, Department of Chemistry, ARSD College, University of Delhi
Units (1, 2.2, 4, 5.2, 5.5, 6.3-6.4, 7.2, 8.2, 9, 10, 12)
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SYLLABI-BOOK MAPPING TABLE
Physical Chemistry - II
Syllabi Mapping in Book
BLOCK -I: SURFACE CHEMISTRY

Unit-1: Adsorption of Gases Unit 1: Adsorption of Gases
Adsorption of gases on solids - Physical and Chemical adsorption –Freundlich, (Pages 1-14);
Langmuir, Temkin and BET isotherms Unit 2: Surface Area Reaction
Unit-2: Surface Area Reaction (Pages 15-40);
Surface area determination - Mechanisms of uni and bimolecular surface reactions Unit 3: Surface Excess
- Langmuir-Hinshelwood and Langmuir-Rideal mechanisms (Pages 41-71)
Unit-3: Surface Excess
Surface excess - Gibbs adsorption isotherm - spreading of a liquid on another -
contact angle – surfactants - micelles and detergents.
BLOCK -II: PHOTOCHEMISTRYAND RADIATION CHEMISTRY

Unit-4: Photophysical Processes Unit 4: Photophysical Processes
Absorption of light by atoms and molecules - photophysical processes of the (Pages 72-96);
electronically excited states - fluorescence and phosphorescence Unit 5: Energy Transfer
Unit-5: Energy Transfer Mechanisms Mechanisms
Energy transfer mechanisms - photosensitization and Chemiluminescence - (Pages 97-115);
actinometers and quantum yield determination Unit 6: Flash Photolysis
Unit-6: Flash Photolysis (Pages 116-132);
Flash photolysis. Study of photochemical reactions - Hydrogen-Halogen Unit 7: Radiation Chemistry
reaction - decomposition of carbonyl compounds (Pages 133-154)
Unit-7: Radiation Chemistry
Radiation chemistry of aqueous solutions-hydrated electron - radiolysis of
water – Pulsed radiolysis.
BLOCK -III: POLYMER CHEMISTRY

Unit- 8: Fundamentals of Polymer Unit 8: Fundamentals of Polymers
Definition, classification of polymers- addition polymerization – type of initiators (Pages 155-171);
– initiator efficiency Unit 9: Stepwise Polymerization
Unit-9: Stepwise Polymerization (Pages 172-189);
Stepwise polymerization – Functionality of monomers and its significance – Unit 10: Kinetics and
Molar masses - Degree of polymerization Mechanism Polymerization
Unit-10: Kinetics and Mechanism polymerization (Pages 190-206);
Kinetics and Mechanism of free radical, cationic and anionic polymerization. Unit 11: Polymerization
Unit-11: Polymerization Techniques Techniques
Various methods of polymerization – solution, bulk, emulsion and suspension (Pages 207-222)
polymerization.
BLOCK -IV: COLLOIDS AND SOLAR ENERGY

Unit-12: Colloids Unit 12: Colloids
Definition, classification, Stability and properties of colloids. (Pages 223-248);
Unit-13: Solar Energy Conversion Unit 13: Solar Energy
Conducting polymers, polymer electrolyte, fire retardant, thermally stable and Conversion: Polymers and
biodegradable polymers. Atom radical polymerization- Basic, mechanism and Polymerization
applicaiton. Dendrimer. (Pages 249-274);
Unit-14: Solar Energy Conversion Unit 14: Solar Energy
Principle, solar panel, photovoltaic cell – dye sensitized solar cell, solar water Conversion: Basic Principles
splitting, artificial photosynthesis, water oxidation and hydrogen evolution (Pages 275-298)
reaction.
CONTENTS
INTRODUCTION
BLOCK I: SURFACE CHEMISTRY

UNIT 1 ADSORPTION OF GASES 1-14
1.0 Introduction
1.1 Objectives
1.2 Adsorption of Gases on Solids
1.2.1 Types of Adsorption
1.2.2 Adsorption Isotherms
1.2.3 Temkin Isotherm
1.3 Answers to Check Your Progress Questions
1.4 Summary
1.5 Key Words
1.6 Self Assessment Questions and Exercises
1.7 Further Readings
UNIT 2 SURFACE AREA REACTION 15-40

2.0 Introduction
2.1 Objectives
2.2 Surface Area Determination
2.3 Mechanisms of Uni and Bimolecular Surface Reactions
2.5 Summary
2.6 Key Words
UNIT 3 SURFACE EXCESS 41-71

3.0 Introduction
3.1 Objectives
3.2 Surface Excess
3.3 Gibbs Adsorption Isotherm
3.4 Spreading of Liquid on Another
3.4.1 Contact Angle
3.5 Surfactant: Micelles and Detergents
3.5.1 Micelle
3.5.2 Detergents
3.7 Summary
3.8 Key Words
BLOCK II: PHOTOCHEMISTRY AND RADIATION CHEMISTRY
UNIT 4 PHOTOPHYSICAL PROCESSES 72-96
4.0 Introduction
4.1 Objectives
4.2 Absorption of Light by Atoms and Molecules
4.2.1 Mechanism for the Absorption of Light
4.2.2 Absorption of Light in Atoms
4.3 Photophysical Processes of the Electronically Excited States
4.4 Fluorescence and Phosphorescence
4.6 Summary
4.7 Key Words
UNIT 5 ENERGY TRANSFER MECHANISMS 97-115

5.0 Introduction
5.1 Objectives
5.2 Energy Transfer Mechanisms
5.3 Photosensitization and Chemiluminescence
5.3.1 Photosensitization
5.3.2 Chemiluminescence
5.4 Actinometers
5.5 Quantum Yield Determination
5.7 Summary
5.8 Key Words
UNIT 6 FLASH PHOTOLYSIS 116-132

6.0 Introduction
6.1 Objectives
6.2 Flash Photolysis
6.3 Study of Photochemical Reactions in Different Areas
6.4 Hydrogen-Halogen Reaction, Decomposition of Carbonyl Compounds
6.6 Summary
6.7 Key Words
UNIT 7 RADIATION CHEMISTRY 133-154

7.0 Introduction
7.1 Objectives
7.2 Radiation Chemistry of Aqueous Solutions-Hydrated Electron
7.3 Radiolysis of Water
7.4 Pulsed Radiolysis
7.6 Summary
7.7 Key Words
BLOCK III: POLYMER CHEMISTRY

UNIT 8 FUNDAMENTALS OF POLYMERS 155-171
8.0 Introduction
8.1 Objectives
8.2 Polymers-Addition Polymerization: Definition and Classification
8.3 Initiators: Types and Initiator Efficiency
8.5 Summary
8.6 Key Words
UNIT 9 STEPWISE POLYMERIZATION 172-189

9.0 Introduction
9.1 Objectives
9.2 Stepwise Polymerization
9.3 Functionality of Monomers and Its Significance – Molar Masses
9.4 Degree of Polymerization
9.6 Summary
9.7 Key Words
UNIT 10 KINETICS AND MECHANISM POLYMERIZATION 190-206

10.0 Introduction
10.1 Objectives
10.2 Kinetics and Mechanism of Free Radical
10.3 Cationic and Anionic Polymerization
10.5 Summary
10.6 Key Words
UNIT 11 POLYMERIZATION TECHNIQUES 207-222
11.0 Introduction
11.1 Objectives
11.2 Methods of Polymerization
11.4 Summary
11.5 Key Words
BLOCK IV: COLLOIDS AND SOLAR ENERGY

UNIT 12 COLLOIDS 223-248
12.0 Introduction
12.1 Objectives
12.2 Colloids: Classification, Stability and Properties
12.2.1 Classification of Colloids
12.2.2 Properties of Colloids
12.2.3 The Stabilisation of the Colloidal State
12.2.4 Application of Collids
12.4 Summary
12.5 Key Words
UNIT 13 SOLAR ENERGY CONVERSION: POLYMERS AND POLYMERIZATION

249-274
13.0 Introduction
13.1 Objectives
13.2 Solar Energy Conversion: Polymers Basics
13.3 Conducting Polymers
13.4 Polymer Electrolyte and Fire Retardant Polymer
13.4.1 Fire Retardant Polymer
13.5 Thermally Stable and Biodegradable Polymers
13.6 Atom Radical Polymerization: Basic Mechanism and Applications
13.6.1 Dendrimer
13.8 Summary
13.9 Key Words
UNIT 14 SOLAR ENERGY CONVERSION: BASIC PRINCIPLES 275-298
14.0 Introduction
14.1 Objectives
14.2 Solar Energy Conversion: Basics And Principles
14.2.1 Principles of Solar Energy Conversion
14.2.2 Principle of Solar Energy: The Photovoltaic Cell Effect Mechanism
14.3 Solar Panel and Photovoltaic Cell
14.4 Artificial Photosynthesis
14.4.1 Solar Water Splitting
14.4.2 Water Oxidation and Hydrogen Evolution Reaction
14.6 Summary
14.7 Key Words
Introduction
INTRODUCTION
Physical chemistry is the study of macroscopic, atomic, subatomic, and particulate

phenomena in chemical systems in terms of the principles, practices, and concepts NOTES
of physics, such as motion, energy, force, time, thermodynamics, quantum
chemistry, statistical mechanics, analytical dynamics and chemical equilibrium. The
term physical chemistry was coined by Mikhail Lomonosov in 1752, when he
presented a lecture course entitled ‘A Course in True Physical Chemistry’ before
the students of Petersburg University.
Physical chemistry often work closely with materials scientists to research
and develop potential uses for new materials. It lies at the interface of chemistry
and physics, in as much as it draws on the principles of physics (especially quantum
mechanics) to account for the phenomena of chemistry. It is also an essential
component of the interpretation of the techniques of investigation and their findings,
particularly because these techniques are becoming ever more sophisticated and
because their full potential can be realized only by strong theoretical backing.
Physical chemistry also has an essential role to play in the understanding of the
complex processes and molecules characteristic of biological systems and modern
mater.
Physical chemistry is traditionally divided into a number of disciplines, but
the boundaries between them are imprecise. Thermodynamics is the study of
transformations of energy. Although this study might seem remote from chemistry,
in fact it is vital to the study of how chemical reactions yield work and heat. Physical
chemistry is essential for understanding the other branches of chemistry. It provides
a basis for understanding the thermodynamic influences, principally, the entropy
changes accompanying reactions that drive chemical reactions forward.
This book, Physical Chemistry II, is divided into four blocks that are further
divided into fourteen units which will help to understand the basic concepts of
adsorption of gases on solids, physical and chemical adsorption (Freundlich,
Langmuir, Temkin and BET isotherms), surface area determination, mechanisms
of uni and bimolecular surface reactions, Langmuir-Hinshelwood and Langmuir-
Riedal mechanisms, surface excess, Gibbs adsorption isotherm, surfactants ,
absorption of light by atoms and molecules, photophysical processes of the
electronically excited states, fluorescence and phosphorescence, energy transfer
mechanisms, photosensitization and chemiluminescence, actinometers and quantum
yield determination, flash photolysis, study of photochemical reactions, hydrogen-
halogen reaction, decomposition of carbonyl compounds, radiation chemistry of
aqueous solutions, hydrated electron, radiolysis of water, pulsed radiolysis.
classification of polymers, addition polymerization, types of initiators, initiator
efficiency, stepwise polymerization, functionality of monomers and its significance,
molar masses, degree of polymerization, kinetics and mechanism of free radical,
cationic and anionic polymerization, various methods of polymerization (solution,
bulk, emulsion and suspension polymerization), definition, classification, stability
and properties of colloids, conducting polymers, polymer electrolyte, fire retardant,
thermally stable and bio-degradable polymers, solar panel, photovoltaic cell –
Self-Instructional
Material 9
Introduction dye sensitized solar cell, solar water splitting, artificial photosynthesis, water
oxidation and hydrogen evolution reaction.
The book follows the self-instruction mode or the SIM format wherein
each unit begins with an ‘Introduction’ to the topic followed by an outline of the
NOTES ‘Objectives’. The content is presented in a simple, organized and comprehensive
form interspersed with ‘Check Your Progress’ questions and answers for better
understanding of the topics covered. A list of ‘Key Words’ along with a ‘Summary’
and a set of ‘Self Assessment Questions and Exercises’ is provided at the end of
the each unit for effective recapitulation.
Self-Instructional
10 Material
Adsorption of Gases
BLOCK - I
SURFACE CHEMISTRY
NOTES
UNIT 1 ADSORPTION OF GASES
Structure
1.0 Introduction
1.1 Objectives
1.2 Adsorption of Gases on Solids
1.4 Summary
1.5 Key Words
1.0 INTRODUCTION
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. This process differs from absorption, in which a fluid,
i.e., the absorbate is dissolved by or permeates a liquid or solid (the absorbent),
respectively. Adsorption is a surface phenomenon, while absorption involves the
whole volume of the material. The term sorption encompasses both processes,
while desorption is the reverse of it.
The process of adsorption is usually studied through graphs know as
adsorption isotherm. It is the graph between the amounts of adsorbate (x) adsorbed
on the surface of adsorbent (m) and pressure at constant temperature. Different
adsorption isotherms have been Freundlich, Langmuir and BET theory.
In this unit, you will study about absorption , physical and chemical
absorption, absorption isotherms, Freundlich, Langmuir, Temkin and BET isotherms
in detail.
1.1 OBJECTIVES
After going through this unit, you will be able to:

 Understand what absorption is
 Explain physical and chemical absorption
 Discuss Freundlich, Langmuir, Temkin and BET isotherms Self-Instructional
Material 1
Adsorption of Gases
1.2 ADSORPTION OF GASES ON SOLIDS
When solids are allowed to remain in contact with a gas, a film of gas molecules
NOTES accumulates on the surface. It was pointed out in the discussion of surface tension
that the molecular forces at the surface of a liquid are unbalanced or unsaturated
than in the bulk. Similarly, molecules or ions at the surface of a solid have unsaturated
or residual forces. Solid and liquid surfaces, therefore, have a tendency to satisfy
their residual forces by attracting onto and retaining on their surfaces, molecules
of gases or other substances with which they come in contact. This results in
higher concentration of molecules on the surface of a solid or liquid than in the
bulk of the medium. This phenomenon is known as adsorption.
The substance on which the adsorption takes place is known as the
adsorbent and the substance which is adsorbed in known as adsorbate.
The phenomenon of adsorption should not be confused with absorption
which refers to one material passing into the bulk of another. For example, water
is adsorbed by a sponge and water vapours are adsorbed by anhydrous calcium
chloride. On the other hand, water vapours are adsorbed by silica gel and acetic
a particular process is adsorption or absorption, the term sorption is used which
includes both absorption and adsorption. Figure 1.1 shows the adsorption of a
gas on a solid surface.
Fig. 1.1: Adsorption of a Gas on a Solid Surface
Adsorption of Gases by Solids

All solids adsorb gases to some measurable extent. The magnitude of adsorption
of gases by solids depends on the nature of the solid and the gas being adsorbed,
the state of subdivision (area) of the solid the temperature and the pressure of the
gas.
It has been observed that those solids which have the largest possible surface
areas are very good adsorbing agents. In fact, larger is the surface area, greater
will be the amount of gas adsorbed. The best adsorbents used in practice are
various kinds of specially prepared carbon (wood, bone and blood charcoals,
Self-Instructional
2 Material
etc). They have large surface areas due to their exceptionally high porosity. In Adsorption of Gases
addition to various kinds of carbon, other good adsorbing substances are silica
gel, alumina, kaolin and certain alumino silicates. The adsorption power of these
substances can further be enhanced by a process called activation. During
NOTES
activation, the adsorbent is heated in steam or air atmosphere to about 1500ºC.
Heating drives out all impurities gasified at that temperature from the pores and
leads to larger free surface for adsorption. Thus, activated charcoal at 24ºC adsorbs
1.48 gram of carbon tetrachloride per gram of charcoal whereas before activation
it, could adsorb only 0.011 gram per gram of charcoal.
Gases which condense more easily are much more strongly adsorbed. Since
it is difficult to determine the surface area of adsorbing agents directly, the mass of
adsorbent is generally taken as a measure of the surface available for adsorption.
Hence adsorption is generally expressed as the amount of substance adsorbed
per unit mass of adsorbing agents.
The amount of adsorbed gas, as a rule, decreases with increase of
temperature at a constant pressure and increases with a fall in temperature. Hence,
according to Le-Chatelier Braun principle, adsorption of a gas by a solid is
accompanied by evaluation of heat which is known as the heat of adsorption.
This has been confirmed by direct experimental evidence. For every gas and solid,
there is some definite heat of adsorption. The extent of adsorption increases with
increase of pressure.
The type of force that holds the adsorbed molecules on the surface has a
considerable effect on certain characteristics, in particular how tightly the molecules
are held and whether the solid will adsorb certain substance more strongly than
others. There are two types of adsorption:
 Physical or Van der Waals Adsorption.
 Chemisorption or Activated Adsorption.
Physical Adsorption: It is characterised by low heats of adsorption of
the order of 5 to 10 kcal per mol of the gas. The process of adsorption is similar
to the condensation of gas on liquid. This suggests that the forces by which the
adsorbed gas molecules are held to the surface of the solid, are similar to the
forces of cohesion of molecules in the liquid state. A rise in temperature will
increase the kinetic energies of molecules and the molecules will leave the surface
thus lowering the extent of adsorption. Another characteristic of physical adsorption
is that the adsorption equilibrium is reversible and is established rapidly. Physical
adsorption is generally observed in the adsorption of various gases on charcoal
and is independent of the chemical nature of the substance being adsorbed.
Chemisorption: In chemisorption adsorption occurs by chemical force
and a chemical bond is formed between the adsorbed molecule and the surface. Self-Instructional
Material 3
Adsorption of Gases Chemisorption is thus highly selective since only certain types of molecules will be
adsorbed by a particular solid. This depends on the chemical properties of gas
and the adsorbent. Chemisorption is accompanied by much higher heat changes
from 10 kcals to 100 kcals per mole. These heat changes are of the same order as
NOTES those involved in chemical reactions. Unlike physical adsorption, chemical
adsorption is not reversible. Hydrogen is strongly adsorbed by metals—nickel,
iron and platinum.
In many cases, it has been observed that adsorption is neither physical nor
chemical but a combination of the two. Some systems show physical adsorption
at low temperatures but as the temperature is raised, physical adsorption changes
into chemical adsorption.
A plot obtained between the amount of substance adsorbed per unit mass of the
adsorbent and the equilibrium (in case of a gas) or concentration (in case of solution)
at constant temperature is known as the adsorption isotherm. Five different types
of adsorption isotherms have been observed in the adsorption of gases on solids.
These are shown in Figure 1.2.
Fig. 1.2: Five Types of Adsorption Isotherms
p0 = Pressure required to condense the gas to liquid.

Type I. Adsorption of nitrogen on charcoal at — 183ºC.
Type II. Adsorption of nitrogen on iron or silica gel at — 195ºC.
Type III. Adsorption of bromine or iodine on silica get at 83ºC.
Type IV. Adsorption of benzene vapours on ferric oxide gel at 50ºC.
Type V. Adsorption of water vapours on charcoal at 100ºC.
In case of chemisorption, only Type I curves are obtained while in case of
Self-Instructional
4 Material
physical adsorption all the five isotherms are observed.
Explanation of Type I Isotherm Adsorption of Gases
The Freundlich Adsorption Isotherm: To show the variation of the amount of

gas adsorbed per unit mass of the adsorbent with pressure at constant temperature,
Freundlich suggested an empirical equation which is known as Freundlich’s NOTES
adsorption isotherm. The equation is
x
= KP1/m ...(1)
m
where x is the mass of gas adsorbed, m the mass adsorbent, p is the
equilibrium pressure and k and n are constants which depend on the nature of the
adsorbate and adsorbent and on the temperature. This equation is applicable only
at low pressures.
In order to test Equation (1), take the logarithms of both sides, when it will
take the form
x 1
log = log k + log p ...(2)
m n
x
According to Equation (2), a plot of log against log p should be a straight
m
1
line with slope equal to and intercept log k as shown in Figure 1.3.
n
Fig. 1.3: Freundlich’s Adsorption Isotherm
It was found that the actual plots were straight lines only at low pressures
and showed a slight curvature at higher pressure, especially at low temperatures.
This indicates that Equation (1) is approximate and cannot be regarded an equation
of general applicability to explain adsorption of gases on solids.
The Langmuir Adsorption Isotherm: Langmuir derived an equation from
theoretical considerations for type I isotherms. He was the first to point out that in
the chemical adsorption of a gas on a solid surface, a layer single molecule in
thickness is formed. He proposed that adsorption process consists of two opposing
actions—(i) condensation of molecules from the gas phase on the surface and (ii)
evaporation of molecules from the surface back into the body of the gas. At
equilibrium the two rates become equal. He derived an equation based on the
following assumptions:
 An adsorbent side adsorbs a layer single molecule in thickness. Self-Instructional
Material 5
Adsorption of Gases
 Adsorption of other molecules on this side is restricted.
 There is no interaction between the adsorbed molecules.
Consider an adsorbing surface exposed to a gas. Molecules of the gas will
NOTES strike the surface and stick for an appreciable time due to condensation while
other gas molecules will evaporate from the surface due to thermal agitation.
Let a fraction  of adsorbing surface be covered by the adsorbed gas
molecules at any instant. Then the fraction (1 – ) of the surface will be bare and
available for adsorption.
If p is the pressure of the gas, then from kinetic theory of gases, rate of
adsorption of gas molecules
= k1p(1 – ) ...(3)
where k1 is proportionality constant.
The rate at which gas molecules evaporate from the surface will depend on
the fraction of the surface covered by the gas molecules.
Therefore, rate of evaporation of gas molecules
= k2 ...(4)
where k2 is another proportionality constant.
At equilibrium, the two rates must be equal so that
k1p(1– ) = k2
k1 p
or = ...(5)
Dividing the numerator and denominator of the right hand side of equation
(5) by k2,
k1 / k2 p
= k 
1  1 p
 k2 
bp
= ...(6)
1  bp
where b is another constant and is equal to k1/k2.
Since the amount of the gas adsorbed per unit mass of the adsorbent, y, is
proportional to the fraction  of the surface covered, i.e.,
y = k
where k is proportionality constant.
Substituting the value of  from equation (6)
kbp
y= 1  bp
ap
= ...(7)
1  bp
Self-Instructional where the constant a = kb.
6 Material
Equation (7) relates the amount of gas adsorbed to the pressure of the gas Adsorption of Gases
at constant temperature and is known as the Langmuir adsorption isotherm. The

constants a and b depend on the nature of the system and on the temperature.
In order to test this isotherm, Equation (7) is rearranged so as to give
NOTES
p 1 b
=    p ...(8)
y a a
Fig. 1.4 Langmuir Adsorption Isotherm
This equation is similar to an equation for a straight line. Hence, if p/y is

plotted against p, a straight line should be obtained with a slope equal to b/a and
intercept equal to 1/a as shown in Figure 1.4.
It was observed in numerous cases that actual curves were straight lines
thus verifying Langmuir adsorption equation.
Consider two extreme cases of Langmuir isotherm:
Case I: When the gas pressure p is very small.
Under these conditions, the factor bp is negligibly small as compared to
unity in the denominator of Equation (7). This equation, therefore, becomes
y = ap
yp ...(9)
which means that at very low pressures, the amount of gas adsorbed is
directly proportional to the pressure.
Case II: When the gas pressure p is very high.
Under these conditions, unity can be neglected in comparison to bp in the
denominator of Equation (7) and this equation becomes
a
y= ...(10)
b
which means that at very high pressure, the amount of gas adsorbed
reaches a constant limiting value.
This situation arises when the surface is nearly completely covered with a
monomolecular layer at high pressures so that change in pressure has a little effect
on the amount of gas adsorbed.
Restriction: Langmuir equation is applicable for smooth, non porous
surfaces, which are not very good adsorbents, and for low values of pressure. If
Self-Instructional
Material 7
Adsorption of Gases the surface is a very good adsorbent and pressure is very high, there are chances
of multilayer formation.
Type II–V Isotherms
NOTES It was pointed out earlier that in physical adsorption, all the five types of adsorpsion
isotherms are observed. Although Langmuir isotherm can satisfactorily explain
type I isotherm, it altogether fails to explain all the five types of curves. It was
proposed that in types II and III, multilayer formation takes place especially the
gas pressure is increased. On this assumption, Brunauer, Emmett and Teller derived
the BET equation for types II and III isotherms. The equation is
p 1 (C  1) p
=  . ...(11)
v( p0  p) vmC (vmC ) p0
Fig. 1.5 Isotherm Plot according to BET Equation
where v and vm are the volumes, reduced to standard conditions, of the gas
adsorbed at pressure p and when the surface is covered with a monomolecular
layer respectively at temperature T, p0 the saturated vapour pressure of the gas at
temperature T and C is a constant approximately equal to (E1 – EL)/RT where E1
is the heat of adsorption of the first layer and EL is the heat of condensation of the gas
to liquid. If E1 > EL, isotherms of type II are observed and if E1 < EL isotherms of
type III are observed.
p p
Equation (11) can be tested by plotting versus . The plot
v p0  p p0
C 1 1
should be a straight line with slope and intercept as shown in Fig. 19.14.
vmC vmC
To explain type IV and V isotherms, it was suggested that in addition to the
multilayer adsorption, condensation of the gas molecules also takes place in the
small pores and capillaries of the adsorbent even at pressure below p0. The
distinction between these two types is again based on the relative magnitudes of
E1 and EL. If E1 > EL, types IV isotherms are observed and if E1 < EL type V
isotherms are observed.
Adsorption from Solution
Solid surfaces can also adsorb solutes from the solution. An application of
Self-Instructional
adsorption from solution is the use of activated charcoal for decolorising sugar
8 Material
solutions. Activated characoal can adsorb colouring impurities on its surface. Other Adsorption of Gases
examples of this type of adsorption are the adsorption of ammonia from ammonium
hydroxide, phenolphthalein from solutions of acids or bases and acetic acid from
its solution in water, etc. by activated charcoal.
NOTES
It has been observed that carbon adsorbs non-electrolytes more readily
from a solution than electrolytes and inorganic solids adsorb electrolytes in
preference to non-electrolytes. This behaviour of adsorbents to attract certain
substances in preference to other substances leads to a phenomenon of negative
adsorption.
Adsorption from solution in most of the cases leads to the formation of layer
single molecule in thickness on the surface of the solid as was observed in the
chemisorption of gas on a solid.
Fig. 1.6 Adsorption of Acetic Acid by Charcoal
This type of adsorption is also affected by temperature and concentration.

The extent of adsorption decreases with increase of temperature and increases
with increase of concentration. In order to represent the variation of extent of
adsorption with concentration, Freundlich suggested an empirical isotherm similar
to Equation (1). This equation is,
x
= kCl/n ...(12)
m
where x and m are the masses of the substance adsorbed and of adsorbent
respectively, C is the equilibrium concentration of the adsorbed substance in the
solution, k and n are empirical constants. Taking logarithms of equation (12), we
get,
x 1
log = log k + log C ...(13)
m n
x
Equation (13) implies that a plot of log against log C should be a straight
m
1
line with slope and intercept log k. Figure 1.6 shows such a plot of a data for
n
the adsorption of acetic acid from aqueous solution at 25ºC.
Temkin adsorption isotherm model contains a factor that explicitly taking into the
account of adsorbent-adsorbate interactions. By ignoring the extremely low and
Self-Instructional
Material 9
Adsorption of Gases large value of concentrations, the model assumes that heat of adsorption (function
of temperature) of all molecules in the layer would decrease linearly rather than in
logarithmic manner with the coverage. As implied in the equation, its derivation is
characterized by a uniform distribution of binding energy (up to some maximum
NOTES binding energy). The fitting was carried out by plotting the quantity sorbed qe
against ln Ce . The constants were determined from the slope and the intercept.
The model is given by the following Equations
Fig. 1.7 Temkin Adsorption Isotherm.
From the Temkin plot shown in Figure 1.7, the following values were
estimated: AT = 0.484 L.g -1 , B = 96.749 J.mol-1 which is an indication of a
physical adsorption and the R2 = 0.9606.
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10 Material
Hutson and Yang applied Temkin isotherm model to confirm that the Adsorption of Gases
adsorption of cadmium ion onto nanozero-valent iron particles follows a

chemisorption process. Similarly, Elmorsi et al. used the Temkin isotherm model
in their investigation of the adsorption of methylene blue onto miswak leaves.
NOTES
Applications of Adsorption
Adsorption finds extensive applications both in the laboratory and in the industry.
Some of the important applications are:
 Adsorption of gases on solids is employed for creating a high vacuum
between the walls of Dewar containers designed for storing liquid air or
liquid hydrogen. This is achieved by placing activated charcoal between the
walls which has already been exhausted to the maximum extent using a
vacuum pump. The activated charcoal will adsorb any gas which may appear
due to glass imperfection or diffusion through the glass.
 Adsorption of gases on solids is also utilized in gas masks which contain an
adsorbent or a series of adsorbents. These adsorbents purify the air for
breathing by adsorbing all the poisonous gases from the atmosphere. In the
same manner, suitable adsorbents can also be employed in the industry for
recovering the solvent vapours from air or particular solvents from the
mixture of other gases.
 Charcoal finds an extensive application in the sugar industry. It is used as a
decolorizer for the purification of sugar liquors. It can also be used for
removing coloring matter from various other types of solutons.
 Adsorption is employed for the recovery and concentrations of vitamins
and other biological substances.
 Adsorption finds extensive applications in chromatography which is based
on selective adsorption of a number of constituents present together in a
solution or gas.
 Adsorption also plays an important role in catalysis.
Check Your Progress

1. What happens when solids are allowed to remain in contact with a gas?
2. What force does molecules or ions have at the surface of a solid?
3. Define adsorption.
4. Distinguish between adsorbent and adsorbate.
5. What property does a gas have which can condense easily?
6. Give a major use of heating.
7. What happens in chemisorption ?
Self-Instructional
Material 11
Adsorption of Gases
1.3 ANSWERS TO CHECK YOUR PROGRESS
QUESTIONS
NOTES 1. When solids are allowed to remain in contact with a gas, a film of gas
molecules accumulates on the surface.
2. Molecules or ions at the surface of a solid have unsaturated or residual
forces.
3. Adsorption is generally expressed as the amount of substance adsorbed
per unit mass of adsorbing agents.
4. The substance on which the adsorption takes place is known as the adsorbent
and the substance which is adsorbed in known as adsorbate.
5. Gases which condense more easily are much more strongly adsorbed.
6. Heating drives out all impurities gasified at that temperature from the pores
and leads to larger free surface for adsorption. Thus, activated charcoal at
24ºC adsorbs 1.48 gram of carbon tetrachloride per gram of charcoal
whereas before activation it, could adsorb only 0.011 gram per gram of
charcoal.
7. In chemisorption adsorption occurs by chemical force and a chemical bond
is formed between the adsorbed molecule and the surface.
1.4 SUMMARY
 When solids are allowed to remain in contact with a gas, a film of gas
molecules accumulates on the surface.
 It was pointed out in the discussion of surface tension that the molecular
forces at the surface of a liquid are unbalanced or unsaturated than in the
bulk.
 The substance on which the adsorption takes place is known as the
adsorbent and the substance which is adsorbed in known as adsorbate.
 The phenomenon of adsorption should not be confused with absorption
which refers to one material passing into the bulk of another. For example,
water is adsorbed by a sponge and water vapours are adsorbed by
anhydrous calcium chloride.
 All solids adsorb gases to some measurable extent. The magnitude of
adsorption of gases by solids depends on the nature of the solid and the gas
being adsorbed, the state of subdivision (area) of the solid the temperature
and the pressure of the gas.
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12 Material
 It has been observed that those solids which have the largest possible surface Adsorption of Gases
areas are very good adsorbing agents. In fact, larger is the surface area,
greater will be the amount of gas adsorbed.
 The best adsorbents used in practice are various kinds of specially prepared
NOTES
carbon (wood, bone and blood charcoals, etc). They have large surface
areas due to their exceptionally high porosity.
 In addition to various kinds of carbon, other good adsorbing substances
are silica gel, alumina, kaolin and certain alumino silicates. The adsorption
power of these substances can further be enhanced by a process called
activation.
 Heating drives out all impurities gasified at that temperature from the pores
and leads to larger free surface for adsorption. Thus, activated charcoal at
24ºC adsorbs 1.48 gram of carbon tetrachloride per gram of charcoal
whereas before activation it, could adsorb only 0.011 gram per gram of
charcoal.
 Physical adsorption is generally observed in the adsorption of various gases
on charcoal and is independent of the chemical nature of the substance
being adsorbed.
 In chemisorption adsorption occurs by chemical force and a chemical bond
is formed between the adsorbed molecule and the surface.
 The Freundlich adsorption isotherm shows the variation of the amount of
gas adsorbed per unit mass of the adsorbent with pressure at constant
temperature, Freundlich suggested an empirical equation which is known
as Freundlich’s adsorption isotherm.
 Langmuir derived an equation from theoretical considerations for type I
isotherms. He was the first to point out that in the chemical adsorption of a
gas on a solid surface, a layer single molecule in thickness is formed.
1.5 KEY WORDS
 Adsorption: Adsorption is the adhesion of atoms, ions or molecules from

a gas, liquid or dissolved solid to a surface.
 Adsorbent: Substance on which the adsorption takes place is known as
the adsorbent.
 Adsorbate: The substance which is adsorbed in known as adsorbate.
 Chemisorption: Chemisorption is a type of adsorption that occurs by
chemical force and a chemical bond which is formed between the adsorbed
molecule and the surface.
Self-Instructional
Material 13
Adsorption of Gases
1.6 SELF ASSESSMENT QUESTIONS AND
EXERCISES
NOTES Short Answer Questions

1. What is adsorption?
2. How many types of adsorptions are there. Write brief note.
3. Expalin with the help of well labelled diagram adsorption of gas on a solid
surface.
4. Brief a note on chemisorption.
5. List in brief the applications of adsorption.
Long Answer Questions
1. Explain the adsorption of gases on solids.
2. Discuss the types of adsorption in detail.
3. What is adsorption isotherm?
4. Give a detailed account on Freundlich adsorption isotherm.
5. Explain in detail about Langmuir adsorption isotherm.
6. Elaborate a note on Temkin adsorption isotherm also give a graph to explain
it.
7. Give a descriptive note on adsorption from solutions.
8. List all the major applications of adsorption.
1.7 FURTHER READINGS
Rohatgi-Mukherjee, K.K. 2008. Fundamentals of Photochemistry. New Delhi:

New Age International (P) Ltd.
Atkins, P.W. 1990. Physical Chemistry. UK: Oxford University Press.
Adamson, A.W. 1982. Physical Chemistry of Surfaces, 4th Edition. New York:
Wiley – InterScience (Division of John Wiley & Sons, Inc.).
Billmeyer Jr., F.W. 2003. Text Book of Polymer Science, 3rd Edition. New
York: John Wiley & Sons, Inc.
Bhatnagar, M.S. 2004. A Textbook of Polymers, Volume I. New Delhi: S. Chand
& Company Ltd.
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14 Material
Surface Area Reaction
UNIT 2 SURFACE AREA REACTION

Structure NOTES
2.0 Introduction
2.1 Objectives
2.2 Surface Area Determination
2.3 Mechanisms of Uni and Bimolecular Surface Reactions
2.5 Summary
2.6 Key Words
2.0 INTRODUCTION
The surface area of a solid object is a measure of the total area that the surface of
the object occupies. The mathematical definition of surface area in the presence of
curved surfaces is considerably more involved than the definition of arc length of
one- dimensional curves, or of the surface area for polyhedra, i.e., the objects
with flat polygonal faces, for which the surface area is the sum of the areas of its
faces.
Surface tension is the tendency of fluid surfaces to shrink into the minimum
surface area possible. At liquid-air interfaces, surface tension results from the greater
attraction of liquid molecules to each other (due to cohesion) than to the molecules
in the air (due to adhesion). The net effect is an inward force at its surface that
causes the liquid to behave as if its surface were covered with a stretched elastic
membrane. Thus, the surface comes under tension from the imbalanced forces,
which is probably where the term 'surface tension' came from. Due to relatively
high attraction of water molecules to each other through a web of hydrogen bonds,
water has a higher surface tension than most other liquids.
In this unit, you will study about surface area determination, mechanism of
uni and bimolecular reactions in detail.
2.1 OBJECTIVES

 Understand what surface area determination is
 Discuss the mechanism of uni and bimolecular reactions
Self-Instructional
Material 15
2.2 SURFACE AREA DETERMINATION
The surface area of a solid object is a measure of the total area that the surface of
NOTES the object occupies. The mathematical definition of surface area in the presence of
curved surfaces is considerably more involved than the definition of arc length of
one- dimensional curve, or of the surface area for polyhedral, i.e., objects with flat
polygonal faces, for which the surface area is the sum of the areas of its faces.
Smooth surfaces, such as a sphere, are assigned surface area using their
representation as parametric surfaces. This definition of surface area is based on
methods of infinitesimal calculus and involves partial derivatives and double
integration.
A general definition of surface area was sought by Henri Lebesgue and
Hermann Minkowski in the twentieth century. Their work defined geometric
measure theory which studies various notions of surface area for irregular objects
of any dimension.
In chemistry, the surface area is considered significant in chemical kinetics.
Increasing the surface area of a substance generally increases the rate of a chemical
reaction. For example, iron in a fine powder will combust, while in solid blocks it
is stable enough to use in structures. For different applications a minimal or maximal
surface area may be desired. For example, when we cut up a piece of a solid, we
increase its surface area. By doing this, we expose more of its particles to attack
by other reactant particles. Therefore we increase the chance of collisions between
reactant particles. Because the collisions become more frequent, the rate of reaction
increases.
Hence, the greater the surface area of a solid reactant, the faster its rate of
reaction.
Thus, as we increase the surface area of the reactants, we increase the rate
of reaction.
Surface Tension
Consider a molecule, A, in the interior of a liquid. It is being attracted by
neighbouring molecules equally in all directions and thus the resultant force on it is
zero. Now consider another molecule, B at the surface. It is experiencing a resultant
force downward because of greater attraction for molecules in the liquid than for
molecules in the vapour above the liquid. This is the case with all the molecules at
the surface. As a result of this inward pull, all the molecules at the surface tend to
go down and in doing so make the liquid behave as if it were enclosed by a
membrane or skin. Thus the surface of the liquid tends to contract to have the
minimum surface area possible. This force in the surface of a liquid is called surface
tension and is defined as the force per unit length exerted at right angles upon a
line of unit length in the surface. The units of surface tension are force per unit
length or is the CGS system dyne per centimeter. It is because of surface tension
Self-Instructional
16 Material
that falling water droplets in vacuum and the mercury particles on a smooth surface Surface Area Reaction
acquire spherical shape (a sphere occupies a smallest area for the given volume).
Since every liquid has a tendency to decrease its surface area, therefore, it is
necessary to do work against the inward pull and to bring molecules from the
interior of the liquid in the surface in order to increase the surface area of the liquid. NOTES
To obtain an expression for this work, consider a film of liquid stretched on a
rectangular wire frame, one side of which is movable.
Let a force, F is applied perpendicular to the movable side to move it against
the force of surface tension. If the wire moves a distance, dx the work done, W is
given by
Fig. 2.1 Force acting on a molecule in a liquid

W = Fdx ...(1)
This causes an increase in the surface area of the film given by
A = 2(l × dx) ...(2)
where l is length of the film. The factor 2 is introduced because there are two sides
of the film.
Fig. 2.2 Calculation of force on a liquid surface

Since the force F is applied against the force of surface of tension acting on
the film, therefore, if  is the force per centimeter along the movable wire, then
F =  × 21 ...(3)
F  Force
=   =
 2l  Unit length
Therefore, W = g  2ldx
=  × A
W Work
or =  ...(4)
A Area
From equation (3), surface tension is defined as the force in dynes acting per
unit length and from equation (4), it can be defined as the work in ergs required to
generate a unit increase in surface area. The units of surface tension are dynes/cm
or ergs/cm2. SI units of surface tension is newton/m.
Self-Instructional
Material 17
Surface Area Reaction Measurement of Surface Tension
The various methods which are commonly employed to determine the surface
tension of a liquid are:
NOTES 1. The Capillary Rise Method: This method is based on the fact that any
liquid such as water which wets the walls of the glass capillary tube will rise in the
tube when the tube is placed in the liquid. On the other hand, if a liquid, such as
mercury which does not wet the walls of the capillary tube will not rise and show
a depression in the level of the liquid in the capillary tube. The rise or falls of a
liquid in a capillary tube is based on the surface tension.
The word capillary means hair in Latin. If the tube were hair thin in the rise
would be large.
Fig. 2.3 Capillary Rise Method for Measuring Surface Tension

Consider a find capillary tube of uniform radius, r, placed in a liquid that wets
the walls of the tube. Because of force of surface tension, , which acts along the
innercircumference of the liquid, liquid will rise. The liquid keeps on rising until
upward force, F1, due to surface tension is balanced by the downward force, F,
due to the weight of the liquid.
Since the force due to surface tension is acting at an angle , known as contact
angle, the upward force F1, is given by
F1 = 2r  cos  ...(5)
If the liquid rises a height h in the tube above the level of the liquid outside, the
downward force, F2 is given by
F2 = r2hdg ...(6)
where d is the density of the liquid and g is the gravitational force. At equilibrium
the two forces are equal.
Therefore, F1 = F2
From Equations (5) and (6)
2r  cos  = r2  hdg
1
or ...(7)
For most liquids  = 0, cos  = 1
1
  = rhdg ...(8)
2
Self-Instructional
A liquid making an angle of 90º, cos 90 = 0
18 Material
2  cos  Surface Area Reaction
h= =0
rdg
would show no capillary rise at all. Mercury whose contact angle again glass is
about 140º shows a capillary depression, i.e.,
NOTES
2g (-ve value)
h=
rdg
The capillary rise phenomenon is not only the basis for an absolute and accurate
means of measuring surface tension but is also one of its major manifestations. The
phenomenon accounts for the general tendency of wetting liquids to enter pores
and fine cracks. The absorption of vapours by porous solids to fill their capillary
channels and the displacement of oil by gas or water in petroleum formations
constitute specific examples of capillary effects. The water proofing of fabrics
involves a direct application of capillary effects. Fabrics are porous materials the
space between amounting to small capillary tubes. If the fibres are coated with
material on which water has contact angle greater than 90º it will oppose the entry
or rise of water into the fabric.
2g(-ve value)
h=
rdg
Example 2.1
The radius of a given capillary is 0.0355 cm. A liquid whose density is 0.866 gram/
cm2 rises to a height of 2.0 cm in the capillary when it is dipped in the liquid.
Calculate the surface tension of the liquid.
Solution: Since  = 1/2 r h dg
Here r = 0.03335 cm, h = 2.0 cm
d = 0.866 gram/cm2 and g = 981
Therefore  = 1/2 × 0.0335 × 2.0 × 0.866 × 981
= 28.46
Thus, surface tension of the liquid = 28.46 dynes/cm.
Example 2.2
At 20ºC, the surface tension of chloroform is 16.2 dynes/cm. The densities of
liquid and gas at the same temperature are 0.1988 gm/cm2 and 0.0110 gram/cm3.
If the radius capillary is 0.105 mm, what would be the height of the liquid in the
capillary, angle of contact being zero?
Solution:
1 r
 = h (dl dv ) gr.
3 3
Here  =162; h = ?
d l = 0.9l88, dv = 0.0110
g = 981
and r = 0.0105 cm
Self-Instructional
Material 19
Surface Area Reaction Substituting these values,
1  0.0105 
16.2= h (0.9188 – 0.0110) 931 × 0.0105
2  3 
or h = 3.46
NOTES
Thus, liquid rises to height of 3.46 cm in the capillary.
2. The Drop-Weight Method: This method is mainly employed to be
compare the surface tensions of two liquids.
In this method, the liquid whose surface tension is to be determined, is allowed
to pass drop by drop through a capillary tube held vertically. Every drop coming
out of the capillary tube grows spherically in size and attains some definite weight.
When the weight of the drop becomes equal to the force of surface tension, acting
along the circumference of the capillary tube, it falls.
The relationship between the weight of the falling drop (W) and surface tension
() is given by the expression
Wg
= ... (9)
2rf
r
where f is a correction factor which is equal to , v being the volume of the
v1/3
drop and r its radius.
In actual practice it is difficult to determine all the factors on the right hand side
of Equation (9). Thus, for convenience, surface tension of two liquids flowing
separately through the same capillary tube, is compared.
If 1 is the surface tension of one liquid and 2 is the surface tension of another
liquid, the two are related by the expression.
1 W1
 ...(10)
2 W2
where Wl and W2 are the weights of drops of liquids 1 and 2 respectively.
The detached drop thus leaves behind a considerable residue of liquid. Table
2.1 gives some values of f.
Table 2.1: Correction Factors f, for the Drop Weight Method
r r
1/3 f 1/3 f
v v
0.30 0.7256 0.80 0.600
0.40 0.6828 0.90 0.5998
0.50 0.6515 1.00 0.6098
0.60 0.6250 1.10 0.6280
0.70 0.6093 1.20 0.6535
Note that the correction is considerable. In practice one forms the drops
within a closed space to avoid evaporation and in sufficient number that the weight
per drop can be determined accurately. It is only necessary to form each drop
slowly during the final stages of its growth.
Self-Instructional
20 Material
The instrument used for the purpose is known as Surface Area Reaction
the stalagmometer and consists of a bubbled capillary

tube as shown in the Figure 2.4. The tube, after it
has been thoroughly washed and dried, is filled by
sucking upto some certain mark X with the liquid NOTES
whose surface tension is to be determined. The liquid
is then allowed to fall very slowly upto mark Y in the
form of drops which are collected in a weighing bottle.
The number of drops falling at the rate of one to two
seconds is counted and their weight is determined. If
W1 and W2 are the mean weights of drops of the two
liquids and 1 and 2 are their surface tension respec-
tively, they are related to each other by Equation
(1.1).
It is more convenient to determine the number of Fig. 2.4 Stalagmometer
drops formed by a definite volume of a liquid than to
determine the weight of the drop.
Let n1 and n2 be the number of drops of equal volumes (say V) of two liquids
1 and 2 of densities d1 and d2 respectively.
The mean weight of drops of liquid 1 is given by
V
W1=  d1 ...(11)
n1
and the mean weight of drops of liquid 2 is given by
V
W2 =  d2 ...(12)
n2
( weight of drop = volume of drop × density)
Therefore, equation (4.22) becomes
V
 d1
W1 n2
1= 
W2 V
 d2
n2
1 dn
or = 1 2 ...(13)
2 d2n1
From Equation (1.3), knowing the surface tension of one liquid, usually called
the reference liquid, the surface tension o the other liquid can be calculated simply
by knowing their densities and the number of drops formed by the equal volume of
the two liquids.
3. The Tensiometric or Torsion Balance Method: In this method, a
platinum ring about 4 cm in circumference is immersed in the liquid to be tested
from the end of the beam of a torsion balance and the force required to separate
the ring from the surface of the liquid is then measured. The force f, required for
this separation, is related to the surface tension of the liquid by the expression.
Self-Instructional
Material 21
Surface Area Reaction f =  × 2(2r) ...(14)
where (2r) is the circumference of the ring of radius r. The factor 2 is
introduced because the force due to surface tension is acting at both the inner and
the outer circumference of the ring.
NOTES
From Equation (14)
= f ...(15)
4 r
So knowing f and r,  can be easily calculated.
This is the quickest method for determining the surface tension of a liquid and
requires only small amounts of liquid.
Table 2.2: Surface tension of liquids at 20ºC
Liquid (10–3 N/m) Liquid (10–3 N/m)
Acetone 23.70 Ethyl Ether 17.01
Benzene 28.85 n-Hexane 18.43
Carbon tetrachloride 26.95 Methyl alcohol 22.61
Ethyl acetate 23.90 Toluene 28.50
Ethyl alcohol 22.75 Water 72.75
Example 2.3:
In the determination of surface tension of a liquid, A, by the drop weight method
using a stalagmometer, A gave 55 drops while water gave 25 drops volume of the
two liquids being the same. The densities of water and A are 0.996 and 0.800 gm/
cm2 respectively and the surface tension of water is 72.0 dynes/cm. What is the
surface tension of A?
Solution:
1 d1n2
Since =
2 d2n1
Here = 72.0 dynes/cm
2
d2 = 0.996
n2 = 25
1 = ?
d1 = 0.800
and n1 = 55 drops
Substituting these values in the equation, we have
0.800  25
1 = 72  = 26.3
0.996  55
Therefore, surface tension of liquid A = 26.3 dynes/cm.
Variation of Surface Tension with Temperature: The surface tensions of all
liquids decrease with increasing temperature and become zero at the critical
Self-Instructional
22 Material
temperature because at the critical temperature, there is no surface of separation Surface Area Reaction
between the liquid and the vapours. To represent the variation of surface tension
of a liquid with temperature, many equations have been proposed. Some of them
are given below:
NOTES
1. Eötvös Equation (1886): According to this equation,
æ M ö2/3
g ççç ÷÷÷ = K(tc – t) ...(16)
çè dl ø÷
where  is the surface tension of the liquid at temperature t and K is a constant
independent of temperature, M, dt and tc are the molecular weight, density and the
2/3
M  M
critical temperature of the liquid. Since 
 is the molar volume, the factor  
 dl   dl 
M 
is proportional to the molar surface area of the liquid and the product, γ  
 dl 
gives the molar surface energy.
From equation (4.28), molar surface energy varies with temperature in a linear
manner and becomes zero at the critical temperature.
2. Ramsay-Shields Equation (1893): The equation proposed by W
  equation and is expressed
Ramsay and J Shields, is a modification over the Evotvos
as:
æ M ö÷2/3
g ççç ÷÷ = (tc – t – 6) ...(17)
çè d ø÷
l
This equation holds good for many liquids. According to this equation, will
be zero at a temperature 6° below the critical point and will become negative at
the critical point.
3. Katayama’s equation: Katayama replaced (tc – 6) by tc in the Ramsay-
Shields equation to obviate the difficulty that  is zero at t = tc – 6 and proposed in
equation (4.30).
2/3
 M 
  = K(tc – t) ...(18)
 dl  dv 
Here dv is the density of vapour above the liquid at temperature t.
4. MacLeod’s Equation (1923): The equation is
= C(dt–dv)4 ...(19)
where dt is the density of the liquid and dv is the density of the vapour—both
measured at the same temperature. C is a constant, characteristic of each liquid
but is independent of temperature.
This equation holds good with accuracy over a large temperature range for
liquids which do not associate or dissociate.
Self-Instructional
Material 23
Surface Area Reaction In Equations (16), (17) and (18), the value of the constant, K, was found to
be 2.12 for all liquids that behave normally. However, those liquids such as water,
alcohol, carboxylic acids, etc., which are associated, gave not only abnormally
low values of K but also showed variation of K with temperature. For some liquids
NOTES which dissociate, the value of K was found to be higher than 2.12.
Interfacial Tension: The surface tension measures against another immiscible
or partially miscible liquid is referred to as interfacial tension. Consider two
immiscible liquids A and B in contact with each other. If A and B are their respective
surface tensions then the interfacial tension AB exists at the boundary between the
two layers. Interfacial tension can be measured by the pure liquids. For instance, in
the drop weight method, the drops of the liquid may be counted in the liquid against
which the interfacial tension is to be measured, the interfacial tension value AB is
generally intermediate between the surface tensions of the two liquids, A and B. It is
given AB = A – B. Sometimes the interfacial tension may be lower than the surface
tension of the either liquid. For example at 20°C, the surface tensions of water and
carbon tetrachloride are 72.75 and 26.8 respectively. Their interfacial tension is
equal to 45.0, which is very nearly equal to the difference of their surface tensions.
But in the case of water and ethyl ether, the interfacial tension at 20°C is 10.7 which
is lower than the surface tensions of water and ethyl ether at the same temperature
(surface tensions of water and ethyl ether at 20°C are 72.75 and 17.0 respectively).
The phenomena of interfacial tension is of considerable importance in connection
with the properties of emulsions, detergents, foams, etc.
The dirty clothes containing dirt and grease can not be cleaned by washing
with water. This is because water does not wet grease. On adding the detergent or
soap to water the molecules of detergent which are hair pin shaped with one end
attracted to water and the other end to molecules of grease oil or wax, tend to
form water oil interfaces. This results in the removal of dirt and greasy matter and
clean the clothes.
Example 2.4:
From the following data
ºC dt g/cm2 dynes/cm
°C 0.927 4.5
20°C 0.772 1.16
Calculate tc for carbon dioxide using Ramsay equation.
Solution. According to Ramsay equation
2/3
 M 
  = K(tc – t – 6)
 di  dl 
M = 44
Substituting the various values from the data at 0°C (273.16 K)
2/3
 44 
4.5   = K[tc – (273.16 + 6)]
Self-Instructional  0.927 
24 Material
or 36.31 = K(tc – 279.16) Surface Area Reaction
Similarly, substituting the various values at 20°C (293.16 K)

2/3
 44 
1.16   = K[tc – (293.16 + 6)]
 0.722  NOTES
or 140.85 = K[tc – (299.16)]
Taking the ratio of the two equations
140.85 (tc  279.16)
=
36.31 (tc  299.16)
or tc = 306.1 K
= 33°C.
Crystallography
Crystallography is the science of crystals which deals with the study of their
development and growth, their external form internal structure and physical prop-
erties. It is based on three fundamental laws:
 Steno’s Law of Constancy of Interfacial Angles.
 Hauy’s Law of Rationality of Indices
 The Law of Symmetry.
1. The Law of Constancy of Interfacial Angles: This law states that for a
given substance, the corresponding faces or planes forming the external surface of a
crystals intersect at a definite angle and that this angle remains constant no matter,
how the faces develop. Commonly it is observed that the crystal planes are unequally
developed so as to produces the faces of variable size and shape; but the angel of
intersection of any two corresponding faces is always found to be the same for any
crystal of the same substance. The instrument employed for the measurement of
interfacial angle is called goniometer.
Hauy’s Law: For any crystal, a set of three coordinate axes can be chosen
is such a way that all the faces of the crystal will either intercept these axes at
definite distances from the origin or be parallel to some of the axis in which case
the intercepts are at infinity. (Refer Figure 2.5).
Fig. 2.5: Identification of lattice planes by Miller indices

Self-Instructional
Material 25
Surface Area Reaction The law of rationality of indices or intercepts proposed by Hauy, states that it
is possible to choose along the three coordinate axes unit distance (a, b, c) not
necessarily of the same length such that the ratio of the three intercepts of any
plane in the crystal is given by (ma : nb : pc) where m, n and p are either integral
NOTES whole numbers including infinity or fractions of whole numbers.
Let us consider the crystals of mineral topaz, for which four different parameters
have the following values:
(1) m = 1 n = 1 p = 1 (2) m = 1 n = 1 p = 
2
(3) m = 1 n = 1 p = (4) m = 2 n = 1 p = 
3
and hence the intercept ratios are
(1) a : b : c (2) a : b :  c
2
(3) a : b : c (4) 2a : b :  c
3
For any particular plane these ratios characterize the plane and may be used
to represent it. The coefficients of a, b and c are known as the Weiss indices
of a plane. However, Weiss indices are rather awkward to use and have
consequently been replaced by Miller’s indices.
The Miller indices of a plane are obtained by taking the reciprocals of the
Weiss coefficients and multiplying throughout by the smallest number that will
express all the reciprocals as integers. Thus, a plane in which the Weiss notation
is given by a : b :  c becomes in the Miller notation a : b : 0 c or simply (110)
since the order a, b, c is understood. Similarly the four planes mentioned above
for topaz are respectively (111), (110), (223) and 120) in the Miller system of
crystal face notation. If the plane makes an intercept on the negative side, say–
a;–b : and c, the Miller indices for the plane would be (1 10), the bar above
indicates the intersection of the plane on the negative side of the axis. The
symbol 1 means minus unity.
Fig. 2.6. The Octahedron with the Front Faces Indexed

The law of rational intercepts may then be stated as : for any crystalline
species there is a set of axes in terms of which all natural occurring faces have
reciprocal intercepts proportional to the small integers (h k l). The Miller nota-
tions of some of the faces of octahedron will have Miller indices (111),
and (1 1 1) the axes being taken mutually at right
(111), (1 11), (11 1), (1 11), (1 1 1)
angles with origin of the centre of the crystal.
The Law of Symmetry: This law states that all crystals of the same substance
Self-Instructional possess the same elements of symmetry. Symmetry in crystals may be with
26 Material
respect to a plane, a line or a point. A crystal is said to have a plane of symmetry Surface Area Reaction
when it is divided by an imaginary plane into two halves such that one is the
mirror image of the other.
A crystal possesses a line of symmetry when it is possible to draw an imaginary
NOTES
line through the centre of the crystal and then revolve the crystal about this line
through 360º in such a way that the crystal appears unchanged more than once. In
fact it is possible to have crystals which appear the same two, three, four or six
times during one complete revolution of 360º. The line is called the axis of
symmetry. Depending upon the number of times a crystal appears unchanged on
revolution is said to possess two, three, four and six fold axes of symmetry.
A crystal is said to have a centre of symmetry, if every face has another identical
face at an equal distance from, the centre. The total number of planes lines and
centres of symmetry of a crystal are called its elements of symmetry. The cube has
the greatest symmetry. It has thirteen axes of symmetry (three four fold, four three
fold and six two fold), nine planes of symmetry and one centre of symmetry, i.e., 23
symmetry elements in all.
Fig. 2.7 Elements of Symmetry of a Cube
Space Lattice
The regularity of crystal structure leads to the idea of space lattice. In order to
explain this concept, let us consider a crystal of NaCl. It consists of a perfectly
regular arrangement of sodium ions and chloride ions.
x. x. x. x.
. x. x. .x. x. x
x. x. x. x.
. x. x. x. x
x = Na+
. = Cl–
Fig 2.8 Space lattice of NaCl
If we represent the position of each Na+ in the crystal by a point (marked x),
the result will be a regular three dimension network of points. This will be the space
lattice of Na+ in the crystal of NaCl. Similarly, there will be a space lattice for Cl– Self-Instructional
Material 27
Surface Area Reaction and the space lattice for NaCl is made up of the interpenetration of Na+ and Cl–
lattices. The symmetry of the combined lattice determines the symmetry of the crystal
as a whole. It may be noted that each lattice point representing the same atom or
ion. The space lattice of a crystal may be considered as built up of a three
NOTES dimensional basic pattern called the unit-cell. The unit-cell is a repeat unit which
will generate the whole pattern in three dimensions. The external appearance of the
crystal is determined by the shape and dimensions of the unit-cell. It can be proved
by geometrical arguments that only fourteen different simple space lattice are
possible, (Refer Figure 2.9).
Fig. 2.9 The Fourteen Bravaislattices

These are called Bravais lattices. All the crystals in the cubic or a regular
system are made up of one or more of three kinds of lattices, (a) the simple cube,
(b) the face centered cube, and (c) the body centered cube. This is shown in
(Refer Figure 2.9).
The actual lattice consists of a repetition of these units cells in three dimensions.
It can be shown from geometrical considerations that thirty-two different
combinations of the elements of symmetry of a crystal are theoretically possible,.
These are referred to as 32 point groups. In conjunction with Bravais lattices,
these point groups lead to 230 different arrangements known as space groups.
Crystal Systems
Fourteen Bravais lattices and the 32 point groups may be divided into seven-
crystal systems for practical convenience. These systems can be determined by
symmetry considerations and the coordinate axes that are used. These are given
in Table 2.4 and are shown in Refer Figure 2.10.
Self-Instructional
28 Material
NOTES
Fig. 2.10 Seven-Crystal Systems
Table 2.4: The crystal system

System Axes Angles Examples
Cubic a=b=c  =  =  = 90º NaCl, Ag
Tetragonal a=b c  =  =  = 90º White tin,
MgF2
Orthorhombic a  b  c  =  =  = 90º HgCl2,
Rhombic
sulphur
Monoclinic abc  =  = 90º,  = 120º Monoclinic
sulphur,
KClO3
Rhombohedral a = b = c  =  =   90º Calcite, Al2O3
Hexagonal a=bc  =  = 90º,  = 120º Mg, Graphite
Triclinic abc  90º CuSO45H2O
Packing of Atoms in Close-packed Structure

There are numerous ways in which a number of spheres of equal size area can be
packed in layer but a relatively small numbers of these recur again and again. Some
of these ways are represented in Figure 2.11.
Self-Instructional
Material 29
NOTES
Fig. 2.11 Several ways of packing spheres

In (1), (2) and (3) are shown three ways in which the first layer might be
arranged. It is clear that there is a least free space between spheres in arrangement
(3). This arrangement is called the closest packed while those of (1) and (2) may
be the beginning of the cubic patterns. In (4) to (9) are shown the ways of putting
additional layers on these first layers. Starting with the cubic pattern of (1), the
successive layers will generate in simple cubic lattice. Each sphere touches the six
adjacent spheres.
The successive layers of the more open pattern (2) gives rise to a body centered
cubic (bcc) lattice as shown in (5) and (8). Each sphere touches its eight nearest
neighbours at the corners of a cube.
In the closest packed arrangement, there are two distinct ways of adding
successive layers of spheres as shown in (8) and (9). In the first case (8) a hexagonal
closest packed (hcp) structure is obtained. The second case of closest packed
spheres (9) leads to the Cubic Closest Packet (CCP) structure in which the until
cell is a Face Centered Cube (FCC). The number of closest neighbours of a
given sphere is known as its coordination number. The hcp and ccp lattices have
coordination numbers of 12 and thus possess the closest packed structure. The
body centered cubic arrangement is less compact and the coordination number is
8.
The packing of spheres in ionic solids is complicated by the fact that the ions
are positively and negatively charged. In a lattice containing ions, it is geometrically
impossible for any ion to have a coordination number greater than 8 if each section
of the structure is to be electrically neutral. The coordination numbers of the re-
spective ions and the type of unit cell in a crystal will be determined by the charges
and the sizes of the ions. One set of ions may be regarded as occupying the lattice
points of a closest packed structure while the other ions occupy the interpenetrat-
ing close-packed (FCC) lattices. The NaCl crystal consists of two interpenetrat-
ing Close-Packed (FCC) lattices. The positions of one lattice are occupied by
positive ions while those of the other are occupied by negative ions. We can
Self-Instructional
30 Material
imagine sodium chloride structure as fcc arrangement of chloride ions which has Surface Area Reaction
expanded sufficiently to permit the sodium ions in the octahedral holes. Every
sodium ion is in contact with six chloride and each chloride iron in turn is in contact
with six sodium ions; 6-6 coordination. The structure of sodium chloride is shown
in Figure 2.12. NOTES
We have discussed structures of metals and ionic crystals in terms of close-
packed arrangement of spheres. If the particles are not spherical, the discussion
will have to be done in a manner appropriate to the shape of the crystals.
Fig. 2.12 Face-Centered Cubic Lattice of Sodium Chloride formed from the
Interpenetration of the two Face Centered Cubic Lattices of the Ions
Example 2.5:
The element chromium exists as a body centered cubic lattices whose unit cell
edges is 2.88 Å. The density of chromium is 7.20 g/cc How many atoms does
52.0 g of chromium contain?
Solution: Volume of unit cell
= (2.88 A)3 = 23.9 A3
Volume of 52.0 g of chromium
52.0 g
= 7.20 g / cc
= 7.22 cm
Number of unit cells in this volume
7.22 cm2
=
23.9 A 3 / unit cc
2 atoms
= 3.02 1023 unit cells
unit cell
= 6.04 × 1022 atoms.
Check Your Progress

1. What is surface tension ?
2. How does molecules acquire spherical shape?
3. What are the different methods that are used to determine the surface
tension of a liquid ?
4. How is rise and fall of a liquid in a capillary tube determined ?
5. Where is drop-weight method used?
Self-Instructional
Material 31
2.3 MECHANISMS OF UNI AND BIMOLECULAR
SURFACE REACTIONS
NOTES A wide variety of rate laws and reaction mechanisms can apply to surface
catalysed reactions. A few of these are considered below.
Unimolecular Decomposition
Examples of unimolecular decomposition reactions include:
1. Decomposition of NH3 to N2 and H2 on metal surfaces
2. Decomposition of phosphine on glass
3. Decomposition of formic acid on glass, Pt, Ag, Au, or TiO2 (in this case
there are two competing reactions: HCOOH  CO + H2O and HCOOH
 CO2+ H2)
Unimolecular surface reactions can often be described by the mechanism
The rate of product formation is k2 A (where A is the surface coverage of

A), and provided k2 << k-1 (i.e., the rate of reaction of adsorbed A molecules is
much greater than the rate of desorption of unreacted A), the Langmuir adsorption
isotherm can be used to determine A, giving
(20)
This type of reaction shows two limiting rate laws, corresponding to the
two extreme behaviours of the Langmuir isotherm:
(a) At low pressure (PA  0), A is very small and proportional to the pressure.
The rate becomes first order in A(g).
rate (low P) = k2KAPA (21)
(b) At high pressures A is approximately equal to unity, and the reaction is
zeroth order
rate (high P) = k2 (22)
Inhibition
A complication in surface reactions arises when a substance other than the reactant
is adsorbed on the surface. This reduces the effective surface area, and therefore
the rate. If the fraction of the surface covered by the reactant (A) is A, and that
covered by the inhibitor is I, we have
(23)
Self-Instructional
32 Material
Example 26: Derive the above equation by setting up Langmuir equations for A Surface Area Reaction
and I (i.e., kAPAN(1-I- A) = where k and k’

are adsorption and desorption rates and N is the number of available surface
sites) and solving for A.
NOTES
The reaction rate, k2 A, is therefore
(24)
If the pressure of the reactant is low compared to that of the inhibitor, so

that the available surface is only sparsely covered by the reactant, then
and
(25)
If, in addition, the inhibitor is very strongly adsorbed, then and
(26)
The reaction rate is then first order in reactant and inversely proportional to
the inhibitor pressure. Special cases of this arise when the inhibitor is a product of
the reaction.
Activation Energies
The rate constant k2 obeys the Arrhenius law, while the temperature dependence
of the equilibrium constant follows the Van’t Hoff relationship. We have
(27 a,b)
If the pressure is low, we know from (21) that the rate is keffPA, where keff =
k2KA. Combining this with the above expressions gives
(28)
i.e., the apparent activation energy is , the true activation energy

E reduced by the heat of adsorption Hads of the reactant. At high pressure Equation
(23) applies and the apparent activation energy is equal to the true activation
energy, as shown below.
Figure 2.12 At low pressure most of the molecules are not adsorbed and
only have to acquire energy E- Hads to cross the activation barrier. At high pressure Self-Instructional
Material 33
Surface Area Reaction most molecules are adsorbed to the surface and have to acquire energy E to cross
the barrier.
When a reaction is inhibited, the activation energy is modified due to the
adsorption energy of the inhibitor. This is due to the fact that a molecule of inhibitor
NOTES
must be desorbed before a reactant molecule can adsorb to the surface. Equations
can be derived in an analagous way to those above.
Bimolecular Reactions
Bimolecular reactions involving surfaces fall into several different categories,
depending on whether one or both molecules are adsorbed on the surface.
Expressions for rates of inhibited reactions can be readily derived in a similar way
to those for unimolecular reactions above. We will consider three types of
bimolecular surface reactions:
(a) Reaction between two Adsorbed Molecules (Langmuir-Hinshelwood
mechanism)
If molecules A and B compete for the same surface sites, then the reaction
can be represented as shown below.
If the rate of reaction between A and B on the surface is much slower than
attainment of the adsorption-desorption equilibrium, then assuming Langmuir
behaviour gives
(29a)
(29b)
Solving for A and B, and setting the reaction rate equal to kAB gives
(30)
Various approximations can now be made, depending on the rel ative

magnitudes of the two equilibrium constants. If one species, say A, is only weakly
adsorbed, so that KA<<KB, then for roughly equal pressures of the two species,
PA  PB, the above expression becomes
(31)
which reduces at high pressure to
(32)
High pressures of B inhibit the reaction by saturating the surface. At low
pressures, when KBPB<<1, we obtain
Self-Instructional
(33)
34 Material
and the rate is directly proportional to PB. A maximum occurs in the rate at Surface Area Reaction
some point in between the high and low pressure cases as the pressure of B is
increased. This maximum rate may be determined by differentiating (11) with
respect to B.
NOTES
(b) Reaction between a Gas Molecule and an Adsorbed Molecule
(Langmuir-Rideal or Eley-Rideal mechanism)
The mechanism is as shown below
Note that we cannot assume that no B adsorbs to the surface. B will still
compete with A for surface sites, and this must be accounted for in the expression
for the rate by the now familiar KBPB term in the denominator. The rate is given by
The Eley-Rideal mechanism does not lead to a maximum in the rate as PA

and/or PB are changed, a property which can be used to distinguish this mechanism
from the Langmuir- Hinshelwood mechanism. Surface combinations of atoms and
free radicals generally occur by Eley-Rideal mechanisms.
(c) Adsorption of two Gases without Mutual Displacement
A third possibility is that reaction occurs between two molecules which adsorb on
different types of surface sites. In this case they do not displace each other from
the surface (i.e., A and B do not compete for surface sites). At equilibrium, we
have
The reaction rate is then
The dependence of rate on PA and PB in this case is very different from that
of the previous two mechanisms, and this type of mechanism can be readily
distinguished by measuring rates over a wide range of pressures. Examples of
processes in which this mechanism is favoured include reaction between hydrogen
and nitrous oxide on gold and reaction between hydrogen and CO2 on tungsten.
Examples
1. Oxidation of CO
O2 undergoes dissociative adsorption on a Pt(III) surface, while CO is strongly
chemisorbed. If O2 is adsorbed first, its surface distribution is quite open.
Subsequent adsorption of CO is therefore possible, and reaction could occur via
either a Langmuir- Hinshelwood or an Eley-Rideal mechanism. Self-Instructional
Material 35
NOTES Since CO is strongly adsorbed, a Langmuir-Hinshelwood mechanism would

seem more likely, and this is confirmed by experiment. Molecular beam studies
have shown that there is a ~1ms time lag between CO arriving at the surface and
CO2 leaving the surface, at a temperature of 440 K. CO2 only adsorbs weakly to
the surface, and so the long time lag can only be explained if the reaction occurs
via a strongly adsorbed CO species.
2. Synthesis of Ammonia
In the Haber-Bosch process, ammonia is formed from reaction between N2 and
H2 using an Fe3O4 catalyst. Both H2 and N2 undergo dissociative adsorption onto
the surface of the catalyst, N2 much more slowly than H2. For a long time it was
not known whether adsorbed H atoms reacted with atomic or molecular N2
adsorbed on the surface. The problem was resolved by an Auger spectroscopy
stu dy, which showed that the number density of adsorbed atomic nitrogen falls
rapidly at higher pressures of H2, indicating that adsorbed N is involved in the
reaction and that dissociative adsorption of N2 is the rate determining step. The
overall reaction mechanism and a potential energy diagram for the process are
shown below.
Check Your Progress

6. Give example for unimolecular decomposition reaction.
7. How is unimolecular surface reaction described ?

QUESTIONS
1. The force in the surface of a liquid is called surface tension and is defined as
the force per unit length exerted at right angles upon a line of unit length in
the surface.
2. The surface tension that tends to falls on water droplets in vacuum and the
mercury particles on a smooth surface acquire spherical shape, i.e., a sphere
Self-Instructional
occupies a smallest area for the given volume.
36 Material
3. The various methods which are commonly employed to determine the surface Surface Area Reaction
tension of a liquid are:

 Capillary rise method
 Drop-weight method NOTES
 Tensiometric or torsion balance method
4. The rise or falls of a liquid in a capillary tube is based on the surface tension.
5. The drop-weight method is mainly employed to be compare the surface
tensions of two liquids.
6. Some of the examples of unimolecular decomposition reactions include:
 Decomposition of NH3 to N2 and H2 on metal surfaces
 Decomposition of phosphine on glass
 Decomposition of formic acid on glass, Pt, Ag, Au, or TiO2 (in this
case there
are two competing reactions: HCOOH  CO + H2O and HCOOH 
CO2 + H2)
7. Unimolecular surface reactions can often be described by the mechanism
2.5 SUMMARY
 The force in the surface of a liquid is called surface tension and is defined as
the force per unit length exerted at right angles upon a line of unit length in
the surface. The units of surface tension are force per unit length or is the
CGS system dyne per centimeter.
 The capillary rise method is based on the fact that any liquid such as water
which wets the walls of the glass capillary tube will rise in the tube when the
tube is placed in the liquid.
 The capillary rise phenomenon is not only the basis for an absolute and
accurate means of measuring surface tension but is also one of its major
manifestations.
 The phenomenon accounts for the general tendency of wetting liquids to
enter pores and fine cracks. The absorption of vapours by porous solids to
fill their capillary channels and the displacement of oil by gas or water in
petroleum formations constitute specific examples of capillary effects.
 The water proofing of fabrics involves a direct application of capillary effects.
Fabrics are porous materials the space between amounting to small capillary
tubes.
Self-Instructional
Material 37
Surface Area Reaction  The drop-weight method is mainly employed to be compare the surface
tensions of two liquids.
 Every drop coming out of the capillary tube grows spherically in size and
attains some definite weight.
NOTES
 When the weight of the drop becomes equal to the force of surface tension,
acting along the circumference of the capillary tube, it falls.
 In tensiometric or torsion balance method a platinum ring about 4 cm in
circumference is immersed in the liquid to be tested from the end of the
beam of a torsion balance and the force required to separate the ring from
the surface of the liquid is then measured.
 Variation of surface tension with temperature of all liquids decrease with
increasing temperature and become zero at the critical temperature because
at the critical temperature, there is no surface of separation between the
liquid and the vapours. CRYSTALLOGRAPHY
 Crystallography is the science of crystals which deals with the study of their
development and growth, their external form internal structure and physical
properties.
 Crystallography is based on three fundamental laws: Steno’s law of constancy
of interfacial angles, Hauy’s law of rationality of indices, and the law of
symmetry.
 The law of constancy of inter facial angles states that for a given substance,
the corresponding faces or planes forming the external surface of a crystals
intersect at a definite angle and that this angle remains constant no matter,
how the faces develop.
 Hauy’s Law states that any crystal or a set of three coordinate axes can be
chosen is such a way that all the faces of the crystal will either intercept
these axes at definite distances from the origin or be parallel to some of the
axis in which case the intercepts are at infinity.
 The law of symmetry states that all crystals of the same substance possess
the same elements of symmetry. Symmetry in crystals may be with respect
to a plane, a line or a point.
 A crystal is said to have a plane of symmetry when it is divided by an
imaginary plane into two halves such that one is the mirror image of the
other.
 A crystal possesses a line of symmetry when it is possible to draw an imaginary
line through the centre of the crystal and then revolve the crystal about this
line through 360º in such a way that the crystal appears unchanged more
than once. In fact it is possible to have crystals which appear the same two,
three, four or six times during one complete revolution of 360º. The line is
called the axis of symmetry.
Self-Instructional
38 Material
 Depending upon the number of times a crystal appears unchanged on Surface Area Reaction
revolution is said to possess two, three, four and six fold axes of symmetry.
 A crystal is said to have a centre of symmetry, if every face has another
identical face at an equal distance from, the centre. The total number of
NOTES
planes lines and centres of symmetry of a crystal are called its elements of
symmetry.
 The regularity of crystal structure leads to the idea of space lattice. in order
to explain this concept, let us consider a crystal of NaCl. it consists of a
perfectly regular arrangement of sodium ions and chloride ions.
 The actual lattice consists of a repetition of these units cells in three
dimensions. It can be shown from geometrical considerations that thirty-
two different combinations of the elements of symmetry of a crystal are
theoretically possible.
 There are numerous ways in which a number of spheres of equal size area
can be packed in layer but a relatively small numbers of these recur again
and again.
 The packing of spheres in ionic solids is complicated by the fact that the
ions are positively and negatively charged.
 In a lattice containing ions, it is geometrically impossible for any ion to have
a coordination number greater than 8 if each section of the structure is to be
electrically neutral.
 The coordination numbers of the respective ions and the type of unit cell in
a crystal will be determined by the charges and the sizes of the ions. One set
of ions may be regarded as occupying the lattice points of a closest packed
structure while the other ions occupy the interpenetrating close-packed
(FCC) lattices.
 e NaCl crystal consists of two interpenetrating close-packed (FCC) lattices.
The positions of one lattice are occupied by positive ions while those of the
other are occupied by negative ions.
2.6 KEY WORDS
 Crystallography: Crystallography is the science of crystals which deals

with the study of their development and growth, their external form internal
structure and physical properties.
 Law of constancy: The law of constancy of inter facial angles states that
for a given substance, the corresponding faces or planes forming the external
surface of a crystals intersect at a definite angle and that this angle remains
constant no matter, how the faces develop.
Self-Instructional
Material 39
Surface Area Reaction  Hauy’s law: Hauy’s law states that any crystal or a set of three coordinate
axes can be chosen is such a way that all the faces of the crystal will either
intercept these axes at definite distances from the origin or be parallel to
some of the axis in which case the intercepts are at infinity.
NOTES
 Law of symmetry: The law of symmetry states that all crystals of the same
substance possess the same elements of symmetry. Symmetry in crystals
may be with respect to a plane, a line or a point.

EXERCISES
Short Answer Questions

1. What is surface area determination?
2. Give short note on surface tension.
3. Brief a note on capillary rise method.
4. Write a short note on interfacial tension.
5. What is crystallography?
1. Elaborate a note on surface area determination also explaining about surface
tension.
2. List the various methods of measurement of surface tension.
3. Explain the variation of surface tension with temperature.
4. Give a detailed note on crystallography and the laws based on it.
5. Discuss in detail about space lattice, crystal systems, packing of atoms in
closed packing structure.
6. Write in detail about the mechanism of uni and bimolecular reactions.

& Company Ltd.
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40 Material
Surface Excess
UNIT 3 SURFACE EXCESS

Structure NOTES
3.0 Introduction
3.1 Objectives
3.2 Surface Excess
3.3 Gibbs Adsorption Isotherm
3.4 Spreading of Liquid on Another
3.4.1 Contact Angle
3.5 Surfactant: Micelles and Detergents
3.5.1 Micelle
3.5.2 Detergents
3.7 Summary
3.8 Key Words
3.0 INTRODUCTION
Surface excess is the difference between the amount of a component actually
present in the system, and that which would be present in a reference system if the
bulk concentration in the adjoining phases were maintained up to the arbitrary
chosen but precisely determined in position dividing surface. Different influences
at the interface may cause changes in the composition of the near- surface layer.
Substances may either accumulate near the surface or, conversely, move into the
bulk. Contact angle is one of the common ways to measure the wettability of a
surface or material. Wetting refers to the study of how a liquid deposited on a solid
(or liquid) substrate spreads out or the ability of liquids to form boundary surfaces
with solid states.
In this unit, you will study about surface excess, Gibbs adsorption isotherm,
spreading of liquid on another, contact angle, surfactants: micelles and detergents
in detail.
3.1 OBJECTIVES
 Describe surface excess
 Understand Gibbs adsorption isotherm
 Explain the phenomenon of spreading of liquid on another
 Analyse the contact angle
 Discuss about surfactants: micelles and detergents Self-Instructional
Material 41
Surface Excess
3.2 SURFACE EXCESS
Surface excess is the difference between the amount of a component actually
present in the system, and that which would be present in a reference system if the
NOTES
bulk concentration in the adjoining phases were maintained up to the arbitrary
chosen but precisely determined in position dividing surface.
Gibbs Isotherm
The Gibbs adsorption isotherm for multi component systems is an equation used
to relate the changes in concentration of a component in contact with a surface
with changes in the surface tension, which results in a corresponding change
in surface energy. For a binary system, the Gibbs adsorption equation in terms of
surface excess is:
Where
Different influences at the interface may cause changes in the composition of the
near-surface layer. Substances may either accumulate near the surface or,
conversely, move into the bulk. The movement of the molecules characterizes the
phenomena of adsorption. Adsorption influences changes in surface
tension and colloid stability. Adsorption layers at the surface of a liquid dispersion
medium may affect the interactions of the dispersed particles in the media and
consequently these layers may play crucial role in colloid stability. The adsorption
of molecules of liquid phase at an interface occurs when this liquid phase is in
contact with other immiscible phases that may be gas, liquid, or solid.
Conceptual Explanation of Equation
Surface tension describes how difficult it is to extend the area of a surface (by
stretching or distorting it). If surface tension is high, there is a large free energy
required to increase the surface area, so the surface will tend to contract and hold
together like a rubber sheet.
There are various factors affecting surface tension, one of which is that
the composition of the surface may be different from the bulk. For example, if
water is mixed with a tiny amount of surfactants (for example, hand soap), the
bulk water may be 99% water molecules and 1% soap molecules, but the topmost
surface of the water may be 50% water molecules and 50% soap molecules. In
this case, the soap has a large and positive ‘surface excess’. In other examples,
the surface excess may be negative: For example, if water is mixed with an inorganic
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42 Material
salt like sodium chloride, the surface of the water is on average less salty and more Surface Excess
pure than the bulk average.

Consider again the example of water with a bit of soap. Since the water surface
needs to have higher concentration of soap than the bulk, whenever the water’s
surface area is increased, it is necessary to remove soap molecules from the bulk NOTES
and add them to the new surface. If the concentration of soap is increased a bit,
the soap molecules are more readily available (they have higher chemical potential),
so it is easier to pull them from the bulk in order to create the new surface. Since
it is easier to create new surface, the surface tension is lowered. The general
principle is:
When the surface excess of a component is positive, increasing the chemical
potential of that component reduces the surface tension.
Next consider the example of water with salt. The water surface is less salty than
bulk, so whenever the water’s surface area is increased, it is necessary to remove
salt molecules from the new surface and push them into bulk. If the concentration
of salt is increased a bit (raising the salt’s chemical potential), it becomes harder to
push away the salt molecules. Since it is now harder to create the new surface, the
surface tension is higher. The general principle is:
When the surface excess of a component is negative, increasing the chemical
potential of that component increases the surface tension.
The Gibbs isotherm equation gives the exact quantitative relationship for these
trends.
Location of Surface and Defining Surface Excess
In the presence of two phases (α and β), the surface (Surface Phase) is located in
between the phase α and phase β. Experimentally, it is difficult to determine the
exact structure of an inhomogeneous surface phase that is in contact with a bulk
liquid phase containing more than one solute. Inhomogeneity of the surface phase
is a result of variation of mole ratios. A model proposed by Josiah Willard
Gibbs proposed that the surface phase as an idealized model that had zero thickness.
In reality, although the bulk regions of α and β phases are constant, the
concentrations of components in the interfacial region will gradually vary from the
bulk concentration of α to the bulk concentration of β over the distance x. This is
in contrast to the idealized Gibbs model where the distance x takes on the value of
zero. The diagram to the right illustrates the differences between the real and
idealized models.
Definition of Surface Excess
In the idealized model, the chemical components of the α and β bulk phases remain
unchanged except when approaching the dividing surface. The total moles of any
component (Examples include: water, ethylene glycol, etc.) remains constant in
the bulk phases but varies in the surface phase for the real system model as shown
below in Figure 3.1.
Self-Instructional
Material 43
Surface Excess
NOTES
Fig. 3.1 Variation in the Concentration of Components in the Surface Phase

of the Real Model
In the real system, however, the total moles of a component varies depending on
the arbitrary placement of the dividing surface. The quantitative measure of
adsorption of the i-th component is captured by the surface excess quantity. The
surface excess represents the difference between the total moles of the i-th
component in a system and the moles of the i-th component in a particular phase
(either α or β) and is represented by:

where Γi is the surface excess of the i-th component, n are the moles, α and β are
the phases, and A is the area of the dividing surface.
Γ represents excess of solute per unit area of the surface over what would be
present if the bulk concentration prevailed all the way to the surface, it can be
positive, negative or zero. It has units of mol/m2.
Relative Surface Excess
Relative Surface Excess quantities are more useful than arbitrary surface excess
quantities. The Relative surface excess relates the adsorption at the interface to a
solvent in the bulk phase. An advantage of using the relative surface excess quantities
is that they don’t depend on the location of the dividing surface. The relative surface
excess of species i and solvent 1 is therefore:
The Gibbs Adsorption Isotherm Equation for  and  Phase

Derivation of the Gibbs adsorption equation:
For a two-phase system consisting of the α and β phase in equilibrium with a
surface S dividing the phases, the total Gibbs free energy of a system can be written
as:
Where G is the Gibbs free energy.
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44 Material
The equation of the Gibbs Adsorption Isotherm can be derived from the Surface Excess
particularization to the thermodynamics of the Euler theorem on homogeneous

first-order forms. The Gibbs free energy of each phase α, phase β, and the surface
phase can be represented by the equation:
NOTES
Where
U is the internal energy
p is the pressure
V is the volume
T is the temperature
S is the entropy
μi is the chemical potential of the i-th component.
By taking the total derivative of the Euler form of the Gibbs equation for
the α phase, β phase and the surface phase:
where A is the cross sectional area of the dividing surface, and γ is the surface
tension.
For reversible processes, the first law of thermodynamics requires that:
where q is the heat energy and w is the work.
Substituting the above equation into the total derivative of the Gibbs energy equation
and by utilizing the result γdA is equated to the non-pressure volume work when
surface energy is c
considered:
by utilizing the fundamental equation of Gibbs energy of a multi component system:
The equation relating the α phase, β phase and the surface phase becomes:
When considering the bulk phases (α phase, β phase), at equilibrium at constant
temperature and pressure the Gibbs–Duhem equation requires
that:
The resulting equation is the Gibbs adsorption isotherm equation:
Self-Instructional
Material 45
Surface Excess The Gbbs adsorption isotherm is an equation which could be considered
an adsorption isotherm that connects surface tension of a solution with the
concentration of the solute.
For a binary system containing two components the Gibbs Adsorption Equation in
NOTES
terms of surface excess is:
Relation between Surface Tension and the Surface Excess

Concentration
The chemical potential of species i in solution depends on the activity a using the
following equation:
where μi is the chemical potential of the i-th component, μio is the chemical
potential of the i-th component at a reference state, R is the gas constant, T is the
temperature, and ai is the activity of the i-th component.
Differentiation of the chemical potential equation results
in:
where f is the activity coefficient of component i, and C is the concentration
of species i in the bulk phase.
If the solutions in the α and β phases are dilute (rich in one particular
component i) then activity coefficient of the component i approaches unity and the
Gibbs isotherm becomes:
Check Your Progress

1. What is surface excess?
2. Give the equation for The Gibbs adsorption equation in terms of surface
excess.
3. What are the factors affecting surface tension?
3.3 GIBBS ADSORPTION ISOTHERM
In the study of adsorption, changes in free energy (G°), enthalpy (H°), and
entropy (S°) are significant for equilibrium constant. The equilibrium constants
for thermodynamic calculation can be derived in different ways. The values of
G°, H°, and S° of adsorption varies because it depends on the method
employed. If the equilibrium constants are derived from other adsorption isotherm
equations or distribution constants for determination of G° then it requires
thorough analysis.
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46 Material
As per standard derivations, if Gibb’s free energy values are negative then Surface Excess
the adsorption process is spontaneous and if it is positive then the adsorption

process is non-spontaneous.
The magnitude of G° measures how distant a reaction is from the
NOTES
equilibrium. If the value of G° is larger, then the reaction is far from the equilibrium
and thus the reaction must shift to reach equilibrium state. In reactions in which the
enthalpy is favourable and entropy is unfavourable, the reaction becomes less
spontaneous (G° increases) until eventually the reaction is not spontaneous (when
G° > 0).
//Gibbs derived a thermodynamic relationship between the surface or interfacial
tension γ and the surface excess Γ (adsorption per unit area). At constant
temperature, in the presence of adsorption, the Gibbs adsorption equation is
dγ = −∑(ni/A)dμI = −∑ΓidμI, , where (ni/A) = Γi is the number of moles of
component I adsorbed per unit area and μI is the chemical potential of the surfactant
solution. For a single surfactant component, the Gibbs adsorption equation is simply
dγ/dlog C = “2.303 Γ RT, where C is the surfactant concentration, R is the gas
constant, and T is the absolute temperatures. The Gibbs adsorption equation allows
one to determine the amount of surfactant adsorption Γ (moles m”2) from a plot of
log γ (the surface tension at the air/water interface or interfacial tension at the
liquid/liquid interface) versus log C.
In thermodynamics, the Gibbs free energy (IUPAC recommended
name, Gibbs energy or Gibbs function, also known as free enthalpy to distinguish
it from Helmholtz free energy) is a thermodynamic potential that can be used to
calculate the maximum of reversible work that may be performed by a thermo-
dynamic system at a constant temperature and pressure (isothermal, isobaric). The
Gibbs free energy (ΔGº = ΔHº-TΔSº) is the maximum amount of non-expansion
work that can be extracted from a thermodynamically closed system (one that can
exchange heat and work with its surroundings, but not matter); this maximum can
be attained only in a completely reversible process. When a system transforms
reversibly from an initial state to a final state, the decrease in Gibbs free energy
equals the work done by the system to its surroundings, minus the work of
the pressure forces.
The Gibbs energy (also referred to as G) is also the thermodynamic potential
that is minimized when a system reaches chemical equilibrium at constant pressure
and temperature. Its derivative with respect to the reaction coordinate of the system
vanishes at the equilibrium point. As such, a reduction in G is a necessary condition
for the spontaneity of processes at constant pressure and temperature.
Properties of Gibbs Free Energy (G)
This function is defined by
G= E – TS + PV ...(1)
This definition may be written in two alternative but equivalent forms which
are frequently employed. First, since H it equivalent to E + PV, hence Self-Instructional
Material 47
Surface Excess G = H – TS ...(2)
Second, since A = E – TS, it follows that
G = A + PV ...(3)
NOTES For a process taking place at constant pressure, the change in free energy is
given by
G = A + P V ...(4)
If, in addition, the temperature is constant, A = –Wm as seen from Equation,
so that equation (4) becomes
G = –(Wm – P V) ...(5)
The quantity Wm represents maximum work obtainable in the given change
and includes all types of work, such as electrical or surface work, in addition to
work of expansion. The latter is equal to P V and so Wm – PdV represents the
reversible work, exclusive of work of expansion, that can be obtained from a
given change in state. The quantity Wm – PdV is referred to as net work.
Thus, –G = Net work
Three decrease in free energy at constant T and P is equal to the maximum
net work available for the given change in state which the process
accompanies.
Again, from complete differential of Equation (2) we get
dG = dH – TdS – SdT ...(6)
But H = E + PV, which on differentiation becomes
dH = dE + PdV + VdP. Also TdS = dE + PdV.
Making use of these identities into Equation (6),
We get
dG= dE + PdV + VdP – dE – PdV – SdT
= –SdT + VdP ...(7)
At constant pressure, dP = 0 and
 G 
  = –S ...(8)
 T P
At constant temperature, dT = 0 and
 G 
  =V ...(9)
 T T
An alternate equation which shows the variation of G with T is obtained by
differentiating the quantity G/T with respect to T at constant P, namely,
  G   G 
   T   T  G
  =  T 2P
 T  P T
= – (G  2TS )
T
But G + TS = H.
Self-Instructional
48 Material
Surface Excess
  G 
   T   H
Therefore,   =– ...(10)
 T  P T2
Isothermal Changes in Free Energy Function: At constant temperature,
dT = 0 and Equation (7) becomes: NOTES
dG = VdP ...(11)
For 1 mole of a perfect gas, PV = RT
or V = RT
P
Substituting this into Equation (11), we get
dG = RT dP ...(12)
P
Integrating between limits, equation (9.38) takes the form:
G2 P2
dP
 dG = RT  P
...(13)
G1 P1
P2
G2 – G1 = RT ln ...(14)
P1
P2
or G = RT ln ...(15)
P1
Generally, the free energy of a gas is related to the standard free energy G°.
This is defined as the free energy of one mole of the gas at one atmosphere pressure.
Equation (15) then becomes
G – G° =
1
or G = G° + RT ln P ...(16)
The Gibbs–Helmholtz Equation
Since G = H – TS
Substituting the value of S from Equation (8), we get
G = H + T  G  ...(17)
 T P
Similarly, substituting the value of S from Equation (6) into equation A = E –
TS, we get
A 
A = E + T   ...(18)
 T V
These two equations are usually regarded as different forms of the Gibbs-
Helmholtz equation. There are also other forms of the Gibbs-Helmholtz equation
which are most widely used.
They are deduced as shown below:
For a given reaction of the type,
Reactants  Products
Self-Instructional
G = Gp – Gr Material 49
Surface Excess where Gp is the sum total of the free energies of all the products and Gr is the
sum total of the free energies of all the reactants.
From Equation (2), we have
Gp= Hp – TSp and Gr = Hr – TSr, so that by
NOTES
substitution
G = (Hp – TSp) – (Hr – TSr)
= (Hp – Hr) – T(Sp – Sr)
or G = H – TS ...(19)
where S and H are respectively the entropy and enthalpy change of the
given isothermal reaction. Further, from Equation (8)
 G p   Gr 
–S = (S p  Sr )     
 T  P  T  P
 (G p  Gr )  ( G ) 
or   =   ...(20)
 T p  T  p
Substituting this result into equation (19), we get
 ( G ) 
G = H + T  ...(21)
 T  P
Similarly, we can deduce the analogous expression
 ( A ) 
A = E + T  ...(22)
 T 
Equations (21) and (22) are alternate forms of the Gibbs-Helmholtz equation.
These equations find numerous practical applications.
Still another form of the Gibbs-Helmholtz equation is obtained by
differentiating G with respect to T at constant P as given below:
T
  G    ( G ) 
   T   T  G
 T  P
  = ...(23)
 T  P T2
But according to Equation (21),
 (  G ) 
T = G – H
 T  P
Therefore, Equation (23) becomes
  ( G )  G  H  G
 T  =
  T2
 T  P
=  H2 ...(24)
T
Example 3.1: One mole of a perfect gas at 27ºC expands isothermally and reversibly
from 10 atm to 1 atm against a pressure that is gradually reduced. Calculate q and W and
each of the thermodynamic quantities, E, G, H, A and S.
Solution: Since the process is carried out isothermally and reversibly from 10
atm to 1 atm against a pressure that is gradually reduced.
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50 Material
Surface Excess
Wmax = – RT RT
P1
= –2.303 RT log
P2
= –(2.303 × 8.314 JK–1 mol–1 × 300.1 K) log 10/1 NOTES
= –5746 J mol–1.
–1
A = Wmax = –5746 J mol
Since the internal energy of a perfect gas is not affected by a change in volume,
E = 0,
q = E – W = 0 + 5746 = 5746 J mol–1
H = E + (PV) = 0 + 0 = 0
Since PV is constant for a perfect gas at constant temperature
1
G =
= –2.303 (8.314 JK–1 mol–1) (300.1 K)

= –5746 J mol–1
qrev 5746 J mol 1
S =   19.15 JK 1mol 1
T 300.1 K
H  G 0  ( 5746 J mol 1 )
S = 
T 300.1 K
= 19.15 JK mol–1
–1
The Gibbs–Duhem Equation

Since dG = VdP – SdT +  µi dni
i
At constant temperature and pressure, this becomes

dG =  µi dni
i
By integrating this Equation, we have

G= µi ni ...(25)
Differentiating Equation (25), we obtain
dG =  (ni dµi  ui dni ) ...(26)
Subtracting Equation (26) from equation (24), we get
 ni dµi = VdP – SdT ...(27)
This is known as the Gibbs-Duhem equation.
At constant temperature and pressure, if the only variation in composition
takes place, Equation (27) takes the form
 ni dµi = 0 (T, P constant) ...(28)
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Material 51
Surface Excess This equation shows that with variations in compositions, the chemical potentials
do not change independently but in a related way. Consider, for example, a system
of two constituents of compositions n1 and n2 respectively. For such a system,
Equation (28) becomes
NOTES
n1dµ1  n2dµ2 = 0 (T, P constant)
or dµ2 = –  n1  dµ1 ...(30)

 n2 
With the help of this equation it is possible to find the change in the chemical
potential dµ of the second constituent by knowing a change in the chemical
2
potential dµ of the first constituent that results due to the variation in composition.
1
Table 3.1 gives various thermodynamic quantities.
Table 3.1 Various Thermodynamic Functions
Definition Function Name
dE = dq + dw E Internal Energy
dqrev
dS = S Entropy
T
H = E + PV H Enthalpy
G = H – TS G Gibbs free Energy
A = E – TS A Helmholtz free energy
(work function)
 G 
µi =   µi Chemical potential
 ni T , P , nj
 H 
Cp =   CP Heat capacity at constant pressure
 T  P
 E 
Cv =   CV Heat capacity at constant volume
 T V
Check Your Progress

4. What happens when a system transforms reversibly from an initial state to
a final state?
5. What is Gibbs free energy ?
6. When is Gibbs free energy minimized?
3.4 SPREADING OF LIQUID ON ANOTHER

Whenever a drop of liquid is placed on the surface of a substrate, the liquid is
expected to evolve until it reaches an equilibrium state. This may require the drop
to either spread and cover the surface or remain as a drop or in some cases even
try to leave the surface. Such a process depends on properties of the surfaces
Self-Instructional
involved as well as the external conditions such as temperature. This field is broadly
52 Material
categorized as wetting and spreading phenomena and aims to determine how a Surface Excess
liquid behaves on the surface of a substrate.

Wetting phenomena are widespread in nature and occur whenever a surface
is exposed to an environment. Understanding why and when a liquid decides to
wet a surface can greatly improve our knowledge of everyday events. Further, this NOTES
information can help in designing new materials and technology. This review is
aimed at providing a basic analysis of wetting and the different phase transitions
that arise during the process. The topics presented here are directly related to the
material covered in phase transitions course during the semester and ties concepts
of discontinuous and continuous phase transitions, and critical exponents to an
excellent real life scenario. Further, this is also a topic of current and growing
interest for both theorists and experimentalists. New developments and recent
experiments are constantly improving our understanding in this field.
Basics of Wetting and Spreading Surface Thermodynamics
When considering a liquid on a surface, there are three systems that come into
play; the liquid, the surface and the surrounding atmosphere which is referred to
as the vapor. The relation between the various surface tensions and the contact
angle was given by Young in Equation (31).
... (31)
Here S, V and L refer to the substrates surface, the vapor and the liquid respectively.
θ is the contact angle as shown in Figure 3.2. Young’s equation in the above form
describes the equilibrium situation when the surface tension forces balance each
other.
Fig. 3.2 Young’s Equation Equates the Surface Tension Forces at Equilibrium
For a given set of surfaces, the corresponding eq can be obtained from the surface
tensions involved. If, for instance SV = SL + LV , then eq = 0 and equilibrium
corresponds to when the liquid is spread across the surface of the substrate. This
situation is referred to as wetting. The other two phases that arise are the dewetting
phase and the partial wetting phase. Though in practice dewetting is rare, from a
thermodynamic point of view both wetting and dewetting are similar under exchange
of surface and the vapor systems. Thus, it suffices to consider and study the wetting
state, which is characterized by a macroscopically thick layer. In the partial wetting
state, the drops on a surface are surrounded by a microscopically thin film adsorbed
at the surface. The three wetting states are shown in Figure 3.3. In typical
experiments film thickness may range from a molecule to several molecules.
Self-Instructional
Material 53
Surface Excess
NOTES
Fig. 3.3 The Three Different Wetting Phases

One can define an equilibrium spreading coefficient Seq to help classify the different
wetting states.
...(32)
Seq above measures the difference between the surface free energy γSV and its
value in the case of complete wetting. Notice that in general Seq d” 0 and Seq =
0 only in the case of complete wetting. When a drop of liquid first encounters a
surface, it is far from the equilibrium state. An initial spreading coefficient may be
defined as follows,
... (33)
Where so is the surface tension of the dry solid substrate. If Si < 0, the drop will
have a finite contact angle i and prefer to remain in a partial wetting state. On the
other hand, if Si > 0 the drop will tend to spread out and wet the surface. An
analysis of the adsorption equation shows that in general Si > Seq. This implies,
whenever Si < 0, this ensures that Seq < 0. Nothing definite can be said about the
sign of Seq, if Si > 0.
Drop Spreading
This part covers some basics of drop spreading. As discussed above, when a
drop is generally placed on a surface, it is far from equilibrium
Consider the simple case of a small viscous droplet on a surface. Here small
implies that the drop radius is less than the capillary length lc, given by
(34)
The capillary number gives the ratio of the viscous and surface tension forces.
(35)
– –
Ca10 5–10 3 in most spreading experiments, η is the liquid viscosity and
U = R1 is the contact line speed. Combining these results one can obtain a
relationship between drop radius and time as give by Tanner’s law Equation (36).
(36)
The rate at which a drop spreads is determined by the interplay between the
surface energies, gravity and dissipation. For small drops the surface free energy
also plays a role
Self-Instructional (37)
54 Material
The first term in this expression corresponds to the liquid-vapor interface due to Surface Excess
the curved nature of the drop and the second term arises due the base area of the
drop being covered by fluid. By inspection of the above equation, it appears that
when Si > 0, spreading would lead to a reduction in the surface free energy.
However, in practice this reduction in free energy is not always converted to NOTES
macroscopic motion of the drop. Instead only some of the molecules near the
contact line may spread out creating a sort of thin precursor film around the drop.
This process uses up the energy that could have gone toward spreading the entire
drop. As Fs reduces, the effective radius R still increases. This causes spreading
coefficient to approach an equilibrium value slowing down the rate of spreading.
In order to compute the power n in Tanner’s equation Equation (36) , one has to
measure the rate of energy dissipation near the contact line
3.4.1 Contact Angle
Contact angle is one of the common ways to measure the wettability of a surface
or material. Wetting refers to the study of how a liquid deposited on a solid (or
liquid) substrate spreads out or the ability of liquids to form boundary surfaces
with solid states. The wetting, as mentioned before is determined by measuring the
contact angle, which the liquid forms in contact with the solids or liquids. The
wetting tendency is larger, the smaller the contact angle or the surface tension is. A
wetting liquid is a liquid that forms a contact angle with the solid which is smaller
then 90º. A non-wetting liquid creates a contact angle between 90º and 180º with
the solid.
Wetting is the ability of a liquid to maintain contact with a solid surface,
resulting from intermolecular interactions when the two are brought together. The
degree of wetting (wettability) is determined by a force balance
between adhesive and cohesive forces. Wetting deals with the three phases of
materials: gas, liquid, and solid. It is now a center of attention in nanotechnology
and nanoscience studies due to the advent of many nanomaterials in the past two
decades.
Wetting is important in the bonding or adherence of two materials. Wetting
and the surface forces that control wetting are also responsible for other related
effects, including capillary effects. There are two types of wetting: non-reactive
wetting and active wetting
A contact angle gives us an indication of how well (or how poorly) a liquid
will spread over a surface. While formulating an ink, contact angles provide a
useful indicator of how a modification to the ink will affect its spreading. A contact
angle can be large or small, depending on the physical properties of the materials
being investigated. Figure 3.4 shows three different droplets on a surface. The
left-most droplet has a large contact angle, as it does not spread over the solid
surface. The right-most droplet has a low contact angle, as it has spread well. This
spreading is know as ‘wetting’, and a droplet either ‘wets’ or ‘dewets’ when
deposited on a surface.
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Material 55
Surface Excess
NOTES
Fig. 3.4 A Varying Contact Angle
Figure 3.5 shows a 2D cross-section of a droplet on a solid surface. Locate the
point at which the droplet outline intersects the solid surface. The angle between
the droplet outline and the solid surface is the contact angle.
Fig. 3.5 A Contact Angle ‘’
Explanation of Contact Angle

Adhesive forces between a liquid and solid cause a liquid drop to spread across
the surface. Cohesive forces within the liquid cause the drop to ball up and avoid
contact with the surface.
The contact angle (θ), as seen in Figure 3.5 is the angle at which the liquid–
vapor interface meets the solid-liquid interface. The contact angle is determined
by the balance between adhesive and cohesive forces. As the tendency of a drop
to spread out over a flat, solid surface increases, the contact angle decreases.
Thus, the contact angle provides an inverse measure of wettability.
A contact angle less than 90° (low contact angle) usually indicates that wetting
of the surface is very favorable, and the fluid will spread over a large area of the
surface. Contact angles greater than 90° (high contact angle) generally means that
wetting of the surface is unfavorable, so the fluid will minimize contact with the
surface and form a compact liquid droplet.
For water, a wettable surface may also be termed hydrophilic and a
nonwettable surface hydrophobic. Superhydrophobic surfaces have contact angles
greater than 150°, showing almost no contact between the liquid drop and the
surface. This is sometimes referred to as the Lotus effect. The table describes
varying contact angles and their corresponding solid/liquid and liquid/liquid
interactions. For non water liquids, the term lyophilic is used for low contact angle
conditions and lyophobic is used when higher contact angles result. Similarly, the
terms omniphobic and omniphilic apply to both polar and apolar liquids.
High-Energy vs. Low-Energy Surfaces
Liquids can interact with two main types of solid surfaces. Traditionally, solid
surfaces have been divided into high-energy solids and low-energy types. The
relative energy of a solid has to do with the bulk nature of the solid itself. Solids
such as metals, glasses, and ceramics are known as ‘hard solids’ because
the chemical bonds that hold them together (for example, covalent, ionic, or metallic)
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56 Material
are very strong. Thus, it takes a large input of energy to break these solids Surface Excess
(alternatively large amount of energy is required to cut the bulk and make two
separate surfaces so high surface energy), so they are termed ‘high energy’. Most
molecular liquids achieve complete wetting with high-energy surfaces.
NOTES
The other type of solids is weak molecular crystals (for example,
fluorocarbons, hydrocarbons, etc.) where the molecules are held together essentially
by physical forces (for example, van der Waals and hydrogen bonds). Since these
solids are held together by weak forces, a very low input of energy is required to
break them, thus they are termed ‘low energy’. Depending on the type of liquid
chosen, low-energy surfaces can permit either complete or partial wetting.
Dynamic surfaces have been reported that undergo changes in surface
energy upon the application of an appropriate stimuli. For example, a surface
presenting photon-driven molecular motors was shown to undergo changes in
water contact angle when switched between bistable conformations of differing
surface energies.
Wetting of Low-Energy Surfaces
Low-energy surfaces primarily interact with liquids through dispersion (van der
Waals) forces. William Zisman produced several key findings:
Zisman observed that cos θ increases linearly as the surface tension (γLV)
of the liquid decreased. Thus, he was able to establish a linear function between
cos θ and the surface tension (γLV) for various organic liquids.
A surface is more wettable when γLV and θ is low. Zisman termed the
intercept of these lines when cos θ = 1, as the critical surface tension (γc) of that
surface. This critical surface tension is an important parameter because it is a
characteristic of only the solid.
Knowing the critical surface tension of a solid, it is possible to predict the
wettability of the surface. The wettability of a surface is determined by the outermost
chemical groups of the solid. Differences in wettability between surfaces that are
similar in structure are due to differences in the packing of the atoms. For instance,
if a surface has branched chains, it will have poorer packing than a surface with
straight chains. Lower critical surface tension means a less wettable material surface.
Check Your Progress

7. What happens when a drop of liquid is placed on the surface of a substrate?
8. What is contact angle?
9. Define the term wetting.
3.5 SURFACTANT: MICELLES AND DETERGENTS

Surfactant, also called surface-active agent, substance such as a detergent that,
when added to a liquid, reduces its surface tension, thereby increasing its spreading
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Surface Excess and wetting properties. In the dyeing of textiles, surfactants help the dye penetrate
the fabric evenly. They are used to disperse aqueous suspensions of insoluble
dyes and perfumes. A term surfactant comes from the word surface active agent.
They are amphiphilic molecules and are thus absorbed in the air-water interface. At
NOTES the interface, they align themselves so that the hydrophobic part is in the air and
hydrophilic part is in water. This causes the decrease in surface or interfacial
tensions.
The surface-active molecule must be partly hydrophilic (water-soluble) and partly
lipophilic (soluble in lipids, or oils). It concentrates at the interfaces between bodies
or droplets of water and those of oil, or lipids, to act as an emulsifying agent, or
foaming agent. Other surfactants that are more lipophilic and less hydrophilic may
be used as defoaming agents, or as demulsifiers. Certain surfactants are germicides,
fungicides, and insecticides.
Surfactants are used in corrosion inhibition, in ore flotation, to promote oil flow in
porous rocks, and to produce aerosols. Surfactants are the most versatile products
of the chemical industry. They are utilized in every industrial area ranging from
household detergents to drilling muds and food items to pharmaceuticals.
Surfactant Basics
Surfactants are amphiphilic molecules that have hydrophobic and hydrophilic parts.
The hydrophobic tail is a hydrocarbon, fluorocarbon or siloxane. Surfactants are
typically classified based on their polar head as the hydrophobic tails are often
similar. If the head group has no charge, the surfactant is called non-ionic. If the
head group has negative or positive charge, it is called anionic or cationic,
respectively. If it contains both positive and negative groups, then the surfactant is
called zwitterionic.
Anionic and non-ionic surfactants are by far the most used surfactant types in
industry. Anionic surfactant find use especially in cleaning product like laundry
detergents and shampoos. Non-inonic surfactants on the other hand are often
used as wetting agents and in food industry. Both cationic and zwitterionic
surfactants are more for special use as they are more expensive to produce.
Table 3.2 Types of Surfactants and Their Uses
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58 Material
Surfactants Absorb at Interfaces Surface Excess
Because of their amphiphilic nature, surfactants absorb at the air-water or oil-

water interface. At the interface, surfactants align themselves so that the hydrophobic
part is in air (or oil) and hydrophilic part in water. NOTES
For simplicity, let’s consider only the air-water interface. The cohesive forces
between the water molecules are very strong making the surface tension of water
high. As surfactants absorb they break these interactions. The intermolecular forces
between surfactant and water molecule are much lower than between two water
molecules and thus surface tension will decrease. When the surfactant concentration
is high, they form micelles. The point at which micelles are formed is called critical
micelle concentration.
The main purpose of the surfactants is to decrease the surface and interfacial
tension and stabilize the interface. Without surfactants washing laundry would be
difficult and many of the food products like mayonnaise and ice cream would not
exist. Thus optimization of surfactants for different applications is highly important
and surface and interfacial tension measurements have the key role in it.
In the bulk aqueous phase, surfactants form masses, such as micelles, where
the hydrophobic tails form the core and the hydrophilic heads are immersed in the
surrounding liquid. Other types of structures can also be formed, such as spherical
micelles or lipid bilayers. The shape of the molecules depends on the balance in
size between hydrophilic head and hydrophobic tail. A measure of this is the HLB,
Hydrophilic-lipophilic balance. Higher HLB surfactants (>10) are hydrophilic (water
loving) and form O/W (Oil-in-water) emulsions. Lipophilic surfactants possess
low HLB values (1-10) and form W/O (water-in-oil) emulsions. Dish detergents,
surfactants for emulsion polymerization, and the following example (SLS = Sodium
Lauryl Sulfate) are high HLB surfactants.
The dynamics of surface active agent adsorption is of great importance for
practical applications such as in emulsifying or coating processes as well as foaming,
where bubbles or drops are rapidly generated and need to be stabilized.
As the interface is created, the adsorption is limited by the diffusion of the
surfactant to the interface, which can result in the kinetics being limited. These
energy barriers can be due to steric or electrostatic repulsions; steric repulsions
form the basis of how dispersants function. Surface rheology of surfactant layers,
are important to the stability of foams and emulsions.
Most surfactants’ tails are fairly similar, consisting of a hydrocarbon chain,
which can be branched, linear, or aromatic. Fluorosurfactants have fluorocarbon
chains. Siloxane surfactants have siloxane chains. Recent advances in surfactant
technology has seen the development of mixed chains or/and complex structures.
There are 4 types of surfactants with a brief review of each as follows.
These classifications are based upon the composition of the polarity of the head
group:
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Material 59
Surface Excess  Nonionic
 Anionic
 Cationic
NOTES  Amphoteric
A non-ionic surfactant has no charge groups in its head. The head of an ionic
surfactant carries a net charge. If the charge is negative, the surfactant is more
specifically called anionic; if the charge is positive, it is called cationic. If a surfactant
contains a head with two oppositely charged groups, it is termed zwitterionic.
Commonly encountered surfactants of each type are listed as follows:
Non-Ionic Surfactant
Many long chain alcohols exhibit some surfactant properties. As the name suggests
they do not have any ions in their molecules, so they are uncharged. To produce
nonionic detergents we react polyethene glycol with stearic acid. There are two
main types of nonionic detergent polyoxyethylene and glycosidic.
Anionic Surfactant
Anionic surfactants contain anionic functional groups at their head, such
as sulfonate, phosphate, sulfate and carboxylates. Alkyl sulfates include ammonium
lauryl sulfate, sodium lauryl and the related alkyl-ether sulfates sodium laureth
sulfate, also known as Sodium Lauryl Ether Sulfate (SLES), and sodium myreth
sulfate. These are the most common surfactants and comprise the alkyl carboxylates
(Soaps), such as sodium stearate. The stearates comprise >50% of the global
usage of surfactants. Many of these find utilization in emulsion polymerization.
Other anionic surfactants include Dioctyl Sodium SulfoSuccinate (DOSS), Per
Fluoro Octane Sulfonate (PFOS), Linear Alkylbenzene Sulfonates (LABs) and
perfluorobutanesulfonate, as well as alkyl-aryl ether phosphates. More specialized
species include sodium lauroyl sarcosinate and carboxylate-based fluorosurfactants
such as Perfluorononanoate, Perfluorooctanoate (PFOA or PFO).
Cationic Surfactant
Cationic surfactants are comprised of a positively charged head. Most of cationic
surfactants find use as anti-microbials, anti-fungals, etc. in HI&I (Benzalkonium
chloride (BAC), CetylPyridinium Chloride (CPC), Benzethonium chloride (BZT).
The cationic nature of the surfactants is not typically consistent with the world of
non-ionic and anionic charges, and they disrupt cell membranes of bacteria and
viruses. Permanently charged quaternary ammonium cations include:
Alkyltrimethylammonium salts: Cetyl Trimethylammonium Bromide (CTAB) and
Cetyl Trimethylammonium Chloride (CTAC).
Zwitterionic Surfactants
Zwitterionic (amphoteric) surfactants have both cationic and anionic centers
attached to the same molecule. The anionic part can be variable and
include sulfonates, as in the sultaines CHAPS (3-[(3-Cholamidopropyl)
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60 Material
dimethylammonio]-1-propanesulfonate). Betaines such as cocamidopropyl betaine Surface Excess
have a carboxylate with the ammonium. The cationic part is based on primary,
secondary, or tertiary amines or quaternary ammonium cations. Zwitterionic
surfactants are often sensitive to pH and will behave as anionic or cationic based
on pH. Fast dry (coacervation) latex traffic paints are based on this concept, with NOTES
a drop in pH triggering the latex in the paint to coagulate.
Reducing Surface Tension
Water, for instance, has a very high natural surface tension (with air) which is what
enables small insects to walk on its surface or a paper clip to float on it. If a few
drops of surfactant were added to the water, a large decrease in the tension between
water and air results, meaning that the insect or the paper clip would sink.
A similarly remarkable effect can be seen in the interaction between dirt (oil
or fat) and water in cleaning processes. Introducing a surfactant, in the form of a
detergent, into the process reduces interfacial tension between the water and soil,
helping to release the dirt and keep it suspended in water so that it can be flushed
or rinsed away.
That is exactly (but not only) what surfactants do every time you wash your
face or hair, do the laundry, clean the dishes, mop the floors or wipe down the
kitchen. In virtually every detergent or cleaning product is a smart surfactant
designed specifically to make the task easier, more effective and more efficient.
Special Molecular Structure
The unique properties of surfactants (i.e., their ability to mobilise and mix naturally
opposing or immiscible substances) are the result of their special molecular structure.
Think of a surfactant molecule as a matchstick, with the thick end being the ‘head’
and the thin end being the ‘tail’. This ‘head’ is water-soluble (hydrophilic) but oil-
-insoluble, whereas the ‘tail’ is water-insoluble (hydrophobic) but oil-soluble. When
added to water as part of a detergent or cleaning formulation, surfactants form
structures called micelles. These micelles are small spheres made of surfactant
molecules where the tails attract and trap oil molecules while the heads of the
micelle suspend them in water.
Fig. 3.16 Molecular Structure of Surfactant Self-Instructional

Material 61
Surface Excess Other Useful Properties
In addition to lowering surface and interfacial tension, and rendering soluble what
is insoluble, surfactants also have a number of other useful properties including:
NOTES  Emulsifying or Dispersing Power
 Wetting
 Foaming
 Suspending/Stabilising Power
These properties are utilised in many everyday products - just imagine a day
without surfactants: toothpaste would not foam while cleaning your teeth, nor rinse
off properly after brushing; there would be no shaving foam at all and not only
would face and sun cream look unappealing, there would be no way for them to
be absorbed on the surface of the skin; and there would be no such thing as a
relaxing foam bath.
But surfactants are not only vital for products found at home. Their unique
characteristics are critical to a diverse range of commercial and industrial processes
that are key to economic development, ranging from metal cleaning and textile
processing to crop care and oil production. Using the right surfactant often makes
products or processes more efficient, less energy, water or resource intensive,
and hence more sustainable
Uses and Benefits
 Surfactants added to cleaning agents, like detergent, allow the detergent to
mix into water, helping cleaning agents remove dirt from the surface being
cleaned. Without surfactants, soaps wouldn’t mix with the water, but would
just roll off the water, making the cleaning process much more difficult.
 Surfactants also are used as an ingredient in lubricants, such as shaving
cream, where they allow razors to easily remove stubble and help limit
irritation.
 Surfactants added to car engine lubricants help keep particles from sticking
to engine parts, allowing the parts to move easily and keep a car in proper
running order.
Applications
The technical performance of surfactants plays a key role in enabling many
applications, and their value chains, to become more sustainable. Smart surfactants
can dramatically improve the overall sustainability of a value chain by promoting
process efficiency and the use of fewer overall resources, whether energy, water
or other materials, and often reducing levels of more hazardous components required.
Some examples where surfactants make a positive contribution to sustainability
include:
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62 Material
 In household cleaning: surfactants have played a decisive role in making Surface Excess
almost all household cleaning jobs easier while providing greater hygiene,
appearance and protection of the surfaces cleaned and reducing the need
for more hazardous chemicals
NOTES
 In laundry detergents: smarter surfactants enable dirt and grime to be
removed at lower washing temperatures - even in cold water - hence
reducing energy and fossil fuel consumption used in the process.
 In insulation production: surfactants are key to the efficiency of manufacturing
processes employed in the production of foam to make insulation boards
and blocks that reduce the energy needed to heat and cool buildings.
 In industrial chemical processing: spraying surfactant solutions onto
powdered chemicals, for example, the latter can be processed more
effectively and more safely.
 In shampoo, liquid soaps and shower gels: surfactants are essential
constituents of these formulations both for mobilising dirt but also allowing
the foam to be easily rinsed off using the minimum amount of water.
 In crop protection: surfactants prevent spray solutions from rolling off the
leaf surface, enable uniform dispersion of the active substance on the leaf
and thus increase the effect of the agents used – the farmers can achieve the
same protection using less chemicals.
3.5.1 Micelle
A micelle is an aggregate (or supramolecular assembly) of surfactant molecules
dispersed in a liquid colloid. A typical micelle in aqueous solution forms an aggregate
with the hydrophilic ’head’ regions in contact with surrounding solvent, sequestering
the hydrophobic single-tail regions in the micelle centre. This phase is caused by
the packing behavior of single-tail lipids in a bilayer. The difficulty filling all the volume
of the interior of a bilayer, while accommodating the area per head group forced
on the molecule by the hydration of the lipid head group, leads to the formation of
the micelle.
This type of micelle is known as a normal-phase micelle (oil-in-water micelle).
Inverse micelles have the head groups at the centre with the tails extending out
(water-in-oil micelle). Micelles are approximately spherical in shape. Other phases,
including shapes such as ellipsoids, cylinders, and bilayers, are also possible. The
shape and size of a micelle are a function of the molecular geometry of its surfactant
molecules and solution conditions, such as surfactant concen-
tration, temperature, pH, and ionic strength. The process of forming micelles is
known as micellisation and forms part of the phase behaviour of many lipids
according to their polymorphism.
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Material 63
Surface Excess
NOTES
Fig. 3.7 Micelle
Fig. 3.8 Cross-Section View of the Structures formed by Phospholipids in

Aqueous Solutions
The above Figure 3.8 illustrates the cross-section view of the structures that can
be formed by phospholipids in aqueous solutions (unlike this illustration, micelles
are usually formed by single-chain lipids, since it is tough to fit two chains into this
shape).
Uses of Surfactants
 When surfactants are present above the Critical Micelle
Concentration (CMC), they can act as emulsifiers that will allow a compound
that is normally insoluble (in the solvent being used) to dissolve. This occurs
because the insoluble species can be incorporated into the micelle core,
which is itself solubilized in the bulk solvent by virtue of the head groups’
favorable interactions with solvent species. The most common example of
this phenomenon is detergents, which clean poorly soluble lipophilic material
(such as oils and waxes) that cannot be removed by water alone. Detergents
clean also by lowering the surface tension of water, making it easier to
remove material from a surface. The emulsifying property of surfactants is
also the basis for emulsion polymerization.
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 Micelle formation is essential for the absorption of fat-soluble vitamins and Surface Excess
complicated lipids within the human body. Bile salts formed in the liver and
secreted by the gall bladder allow micelles of fatty acids to form. This allows
the absorption of complicated lipids (for example, lecithin) and lipid-soluble
vitamins (A, D, E, and K) within the micelle by the small intestine. NOTES
 During the process of milk-clotting, proteases act on the soluble portion
of caseins, ê-casein, thus originating an unstable micellar state that results in
clot formation.
 Micelles can also be used for targeted drug delivery as gold nanoparticles
3.5.2 Detergents
Detergents are amphipathic molecules that contain both polar and hydrophobic
groups. These molecules contain a polar group (head) at the end of a long
hydrophobic carbon chain (tail). In contrast to purely polar or non-polar molecules,
amphipathic molecules exhibit unique properties in water (Refer Figure 3.9). Their
polar group forms hydrogen bonds with water molecules, while the hydrocarbon
chains aggregate due to hydrophobic interactions. These properties allow detergents
to be soluble in water. In aqueous solutions, they form organized spherical structures
called micelles, each of which contain several detergent molecules. Because of
their amphipathic nature, detergents are able to solubilize hydrophobic compounds
in water. Incidentally, one of the methods used to determine the CMC relies on the
ability of detergents to solubilize a hydrophobic dye. Detergents are also known
as surfactants because they decrease the surface tension of water.
Fig. 3.9 A Detergent-Micelle in Water
Often we use the words ‘soap’ and ‘detergent’ interchangeably, but really
they’re quite different things. A detergent is a chemical substance you use to break
up and remove grease and grime, while soap is simply one kind of detergent.
Soap has a long history and was originally made from purely natural products like
goat’s fat and wood ash. Today, detergents are more likely to be a mixture of
synthetic chemicals and additives cooked up in a huge chemical plant and, unlike
traditional soap, they’re generally liquids rather than solids. Detergents are used in
everything from hair shampoo and clothes washing powder to shaving foam and
stain removers. The most important ingredients in detergents are chemicals called
surfactants—a word made from bits of the words surface active agents.
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Surface Excess The Way Detergents Work
The cleverest part of a washing machine isn’t the drum or the drive belt, the electric
motor that spins it around or the electronic circuit that controls the program: it’s
the detergent (soap powder or liquid) you put in right at the start. Water alone
NOTES
can’t clean clothes because it won’t attach to molecules of grease and dirt. The
surfactants it contains are made of molecules that have two different ends. One
end is strongly attracted to water; the other is attracted to oily substances like
grease.
When you wash your clothes in a washing machine the following steps occur:
 During the wash cycle, the surfactant (represented here by the orange blob)
mixes with water.
 The grease-loving ends of the surfactant molecules start to attach themselves
to the dirt on your jeans (shown by the brown blob on the leg). The tumbling
motion beats your jeans about and breaks the dirt and grease into smaller,
easier-to-remove pieces.
 During the rinse cycle, water molecules (blue blob) moving past attach
themselves to the opposite, water-loving ends of the surfactant molecules.
 The water molecules pull the surfactant and dirt away from the jeans. During
the final spin, the dirty water flushes away, leaving your jeans clean again!
Chemicals in Detergents
Surfactants aren’t the only thing in detergents; look at the ingredients on a typical
detergent bottle and you’ll see lots of other chemicals too. In washing detergents,
you’ll find optical brighteners (which make your clothes gleam in sunlight). Biological
detergents contain active chemicals called enzymes, which help to break up and
remove food and other deposits. The main enzymes are proteases (which break
up proteins), lipases (which break up fats), and amylases (which attack starch).
Other ingredients include perfumes with names like ‘limone’, while household
cleaning detergents contain abrasive substances, such as chalk to help scour away
things like burned-on cooker grease and bath-tub grime.
Check Your Progress

10. Give an application of surfactant.
11. What are non-ionic, anionic and zwitterionic surfactants.
12. What is the main purpose of surfactants?
13. What are micelles?
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Surface Excess
QUESTIONS
1. Surface excess is the difference between the amount of a component actually NOTES
present in the system, and that which would be present in a reference system
if the bulk concentration in the adjoining phases were maintained up to the
arbitrary chosen but precisely determined in position dividing surface.
2. The Gibbs adsorption equation in terms of surface excess is:
Where
3. There are various factors affecting surface tension, one of which is that
the composition of the surface may be different from the bulk. For example,
if water is mixed with a tiny amount of surfactants (for example, hand soap),
the bulk water may be 99% water molecules and 1% soap molecules, but
the topmost surface of the water may be 50% water molecules and 50%
soap molecules.
4. When a system transforms reversibly from an initial state to a final state, the
decrease in Gibbs free energy equals the work done by the system to its
surroundings, minus the work of the pressure forces.
5. The Gibbs free energy (ΔGº = ΔHº-TΔSº) is the maximum amount of non-
expansion work that can be extracted from a thermodynamically closed
system (one that can exchange heat and work with its surroundings, but not
matter); this maximum can be attained only in a completely reversible process.
6. The Gibbs energy (also referred to as G) is also the thermodynamic potential

that is minimized when a system reaches chemical equilibrium at constant
pressure and temperature. Its derivative with respect to the reaction
coordinate of the system vanishes at the equilibrium point. As such, a
reduction in G is a necessary condition for the spontaneity of processes at
constant pressure and temperature.
7. Whenever a drop of liquid is placed on the surface of a substrate, the liquid
is expected to evolve until it reaches an equilibrium state. This may require
the drop to either spread and cover the surface or remain as a drop or in
some cases even try to leave the surface. Such a process depends on
properties of the surfaces involved as well as the external conditions such
as temperature. This field is broadly categorized as wetting and spreading
phenomena and aims to determine how a liquid behaves on the surface of a
substrate.
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Material 67
Surface Excess 8. Contact angle is one of the common ways to measure the wettability of a
surface or material. Wetting refers to the study of how a liquid deposited on
a solid (or liquid) substrate spreads out or the ability of liquids to form
boundary surfaces with solid states.
NOTES 9. Wetting is the ability of a liquid to maintain contact with a solid surface,
resulting from intermolecular interactions when the two are brought together.
The degree of wetting (wettability) is determined by a force balance
between adhesive and cohesive forces. Wetting deals with the three phases
of materials: gas, liquid, and solid.
10. Surfactants are used in corrosion inhibition, in ore flotation, to promote oil
flow in porous rocks, and to produce aerosols. Surfactants are the most
versatile products of the chemical industry. They are utilized in every industrial
area ranging from household detergents to drilling muds and food items to
pharmaceuticals.
11. Surfactants are amphiphilic molecules that have hydrophobic and hydrophilic
parts. The hydrophobic tail is a hydrocarbon, fluorocarbon or siloxane.
Surfactants are typically classified based on their polar head as the
hydrophobic tails are often similar. If the head group has no charge, the
surfactant is called non-ionic. If the head group has negative or positive
charge, it is called anionic or cationic, respectively. If it contains both positive
and negative groups, then the surfactant is called zwitterionic.
12. The main purpose of the surfactants is to decrease the surface and interfacial
tension and stabilize the interface. Without surfactants washing laundry would
be difficult and many of the food products like mayonnaise and ice cream
would not exist. Thus optimization of surfactants for different applications is
highly important and surface and interfacial tension measurements have the
key role in it.
13. A micelle is an aggregate (or supramolecular assembly) of surfactant
molecules dispersed in a liquid colloid. A typical micelle in aqueous
solution forms an aggregate with the hydrophilic ’head’ regions in contact
with surrounding solvent, sequestering the hydrophobic single-tail regions
in the micelle centre. This phase is caused by the packing behavior of single-
tail lipids in a bilayer.
3.7 SUMMARY
 Surface excess is the difference between the amount of a component actually

present in the system, and that which would be present in a reference system
if the bulk concentration in the adjoining phases were maintained up to the
arbitrary chosen but precisely determined in position dividing surface.
 The Gibbs adsorption isotherm for multi component systems is an equation
used to relate the changes in concentration of a component in contact with
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a surface with changes in the surface tension, which results in a corresponding Surface Excess
change in surface energy.

 Adsorption influences changes in surface tension and colloid stability.
Adsorption layers at the surface of a liquid dispersion medium may affect
NOTES
the interactions of the dispersed particles in the media and consequently
these layers may play crucial role in colloid stability.
 In homogeneity of the surface phase is a result of variation of mole ratios. A
model proposed by Josiah Willard Gibbs proposed that the surface phase
as an idealized model that had zero thickness.
 The wetting, as mentioned before is determined by measuring the contact
angle, which the liquid forms in contact with the solids or liquids. The wetting
tendency is larger, the smaller the contact angle or the surface tension is.
 Wetting is the ability of a liquid to maintain contact with a solid surface,
resulting from intermolecular interactions when the two are brought together.
The degree of wetting (wettability) is determined by a force balance
between adhesive and cohesive forces.
 A contact angle gives us an indication of how well (or how poorly) a liquid
will spread over a surface. While formulating an ink, contact angles provide
a useful indicator of how a modification to the ink will affect its spreading.
 Adhesive forces between a liquid and solid cause a liquid drop to spread
across the surface. Cohesive forces within the liquid cause the drop to ball
up and avoid contact with the surface.
 Contact angles greater than 90° (high contact angle) generally means that
wetting of the surface is unfavorable, so the fluid will minimize contact with
the surface and form a compact liquid droplet.
 Liquids can interact with two main types of solid surfaces. Traditionally,
solid surfaces have been divided into high-energy solids and low-energy
types. The relative energy of a solid has to do with the bulk nature of the
solid itself.
 Solids such as metals, glasses, and ceramics are known as ‘hard solids’
because the chemical bonds that hold them together (for example, covalent,
ionic, or metallic) are very strong.
 Surfactant, also called surface-active agent, substance such as
a detergent that, when added to a liquid, reduces its surface tension, thereby
increasing its spreading and wetting properties. In the dyeing of textiles,
surfactants help the dye penetrate the fabric evenly.
 Anionic and non-ionic surfactants are by far the most used surfactant types
in industry. Anionic surfactant find use especially in cleaning product like
laundry detergents and shampoos.
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Surface Excess  Non-inonic surfactants on the other hand are often used as wetting agents
and in food industry. Both cationic and zwitterionic surfactants are more for
special use as they are more expensive to produce.
 Detergents are amphipathic molecules that contain both polar and
NOTES
hydrophobic groups. These molecules contain a polar group (head) at the
end of a long hydrophobic carbon chain (tail). In contrast to purely polar or
non-polar molecules, amphipathic molecules exhibit unique properties in
water.
3.8 KEY WORDS
 Surface excess: Surface excess is the difference between the amount of a

component actually present in the system, and that which would be present
in a reference system if the bulk concentration in the adjoining phases were
maintained up to the arbitrary chosen but precisely determined in position
dividing surface.
 Wetting: Wetting is the ability of a liquid to maintain contact with
a solid surface, resulting from intermolecular interactions when the two are
brought together.
 Surfactant: Surfactant, also called surface-active agent, substance such
as a detergent that, when added to a liquid, reduces its surface tension,
thereby increasing its spreading and wetting properties.
 Non-ionic surfactant: If the polar head group has no charge, the surfactant
is called non-ionic.
 Anionic surfactant: If the polar head group has negative or positive charge,
it is called anionic or cationic, respectively.
 Zwitterionic: If polar head contains both positive and negative groups,
then the surfactant is called zwitterionic.

EXERCISES
1. Write a brief note on Gibbs isotherm.
2. Explain the conceptual explanation of equation of Gibbs isotherm.
3. Brief a note on location of surface.
4. Give short note on surface excess.
5. Write a brief note on surface thermodynamics.
6. Write in short about drop spreading.
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Long Answer Questions Surface Excess
1. Expalin in detail about surface excess.

2. Discuss about Gibbs adsorption isotherm.
3. How is spreading of liquid on another carried out? Discuss. NOTES
4. Write in detail about contact angle.
5. Explain in detail about the surfactants. Also write about micelles and
detergents in detail.
6. Explain with the help of table the types of surfactants and their uses.
7. Draw a well labelled diagram of cross-section view of the structures formed
by phospholipids in aqueous solutions.

& Company Ltd.
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Material 71
Photophysical Processes
BLOCK - II
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
NOTES
UNIT 4 PHOTOPHYSICAL
PROCESSES
Structure
4.0 Introduction
4.1 Objectives
4.2 Absorption of Light by Atoms and Molecules
4.3 Photophysical Processes of the Electronically Excited States
4.4 Fluorescence and Phosphorescence
4.6 Summary
4.7 Key Words
4.0 INTRODUCTION
Photochemical reaction, a chemical reaction initiated by the absorption of energy in
the form of light. The consequence of molecules’ absorbing light is the creation
of transient excited states whose chemical and physical properties differ greatly
from the original molecules. These new chemical species can fall apart, change to
new structures, combine with each other or other molecules, or transfer
electrons, hydrogen atoms, protons, or their electronic excitation energy to other
molecules. Excited states are stronger acids and stronger reductants than the
original ground states.
Photochemical reactions and the properties of excited states are also critical
in many commercial processes and devices. Photography and xerography are both
based upon photochemical processes, while the manufacture of semiconductorchips
or the preparation of masks for printing newspapers relies on UV light to destroy
molecules in selected regions of polymer masks.
The formalism for the absorption of light in the simplest case starts with a
beam of light of intensity I of photons that has just penetrated into a material with
a uniform concentration of absorbing pigments. We ignore reflection and refraction.
The photons penetrate into the material and are absorbed at different depths The
mechanism for absorption is that a photon transfers all its energy to an electron in
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72 Material
In this unit, you will study about absorption of light by atoms and molecules, Photophysical Processes
photophysical processes of the electronically excited states and fluorescence and

phosphorescence in detail.
NOTES
4.1 OBJECTIVES
 Explain absorption of light by atoms and molecules
 Discuss the photophysical processes of the electronically excited states
 Understand what fluorescence and phosphorescence is
4.2 ABSORPTION OF LIGHT BY ATOMS AND

MOLECULES
The importance of photochemistry as a branch of science lies principally in the

fact that it provides the chemical potential which is necessary for biological chemistry
to operate. From its earliest biological stages, the chemical origins of life were
almost certainly photochemical reactions and the food and fuel of life, today is
provided by photosynthesis. The discovery of laser has further helped in the growth
of photochemistry. Earlier we have seen that in order to initiate a chemical reaction,
the reactant molecules must overcome an energy barrier. The energy required to
break the chemical bonds involved in the reaction, is usually supplied in the form
of thermal energy. However, other forms of energy, such as light and sound, have
also been used to initiate chemical reactions. The branch of chemistry which deals
with the study of chemical reactions produced directly or indirectly by light is
called photochemistry. Here we are mainly concerned with the radiation lying in
visible and ultra-violet regions, i.e., the wavelength range between 1000 to Å
2000 Å. Photochemical reactions receive their activation by the absorption of
photons of light molecules. Radiation chemistry comprises the study of chemical
effects produced by ionizing radiations. The term ionizing radiations includes alpha,
beta, gamma and X-rays. There are many type of reactions which are brought
about by exposure to light, such as oxidation, reduction, synthesis and
polymerization reactions.
The Absorption of Light
When a beam of monochromatic radiation falls upon a system, it can be transmitted,
refracted, scattered or absorbed. Grothuss and Draper in 1818 established a
relationship between the light absorbed and the chemical change occurring in a
photochemical reaction. According to this law, ‘Only the light that is absorbed by
a substance is effective in producing a photochemical change.’ This is also
sometimes referred to as the principle of photochemical activation. The converse
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Photophysical Processes of the law is not true. All absorbed light does not bring about chemical action. For
example light is strongly absorbed by solutions of potassium permanganate, but
no chemical effect is produced. The fraction of the incident light absorbed by a
homogeneous medium depends on the depth or the thickness of the medium. This
NOTES is known as Lambert’s law which states that when a beam of monochromatic
radiation passes through a homogeneous absorbing medium, equal fractions of the
incident radiation are absorbed by successive layers of equal thickness of the light
absorbing substance. It can be expressed as
dl
– = a. dx ...(1)
I
where l is the intensity of light and x is the thickness of the medium, a is
called the absorption coefficient. On integration, Equation (1) gives
I = I0e–ax ...(2)
with the boundary condition I = I0 at x = 0. The intensity Ia, of the light
absorbed is given by
Ia = I0 – I
Ia = I0 – I0e–ax
or Ia = I0 (l –e–ax) ...(3)
When the absorbing medium is solution or gas, the relationship between the
intensities of the incident and transmitted radiations is given by Beer’s law, which
states that equal fractions of the incident radiation are absorbed by equal changes
in concentration of the absorbing substance in a path of constant length; that is,
Ia = I0e–Cx ...(4)
where c is the molar concentration and  is the molar extinction coefficient.
The amount of light absorbed is
Ia = I0 – I0e–Cx
= I0(1– e –Cx) ...(5)
The Beer’s law is valid only in dilute solution and when monochromatic light
is used. The extinction coefficient  varies a great deal from substance to substance
and also with the wavelength of the light used. The nature and position of the
absorption band determines the colour of the substance.
The formalism for the absorption of light in the simplest case starts with a beam of
light of intensity I of photons that has just penetrated into a material with a uniform
concentration of absorbing pigments. We ignore reflection and refraction. The
photons penetrate into the material and are absorbed at different depths (Refer
Figure 4.1).
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NOTES
Fig. 4.1 Schematic of Light Rays Penetrating to Different Depths into a Photon
Absorbing Material
The mechanism for absorption is that a photon transfers all its energy to an electron
in the absorbing material. The photon is ‘lost’ from the light beam as it is absorbed
in a single event. The electron is excited by the gain in energy to a higher energy
state in the electron configuration around the atom. This single-event transfer of
photon energy to an electron and the disappearance of the photon is closely related
to the photoelectric effect where the electron is ejected from the material in a
single event. The electron is ejected from the atom by the absorption of an x-ray.
This loss of an electron leaves the atom in an excited state.
Fig. 4.2 Light Incident on a Light Absorbing Material

The above figure shows light incident on a light absorbing material that is represented
by a stack of equivalent thickness, t, layers. The length of the arrows decrease as
the light penetrate showing the decreasing intensity of light.
The decrease in intensity of the light or photon flux as the beam penetrates
into the material can be visualized if we separate the absorbing material into a set
of thin, equal thickness slices of thickness t (Refer Figure 4.2). The material is
homogeneous and the thickness t is chosen so that only a small fraction of the light
is absorbed in passing through the layer. The symbol A is used to denote the
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Photophysical Processes fraction absorbed. The fraction of light absorbed in the first layer is (1-A) times
the incident intensity. For example, if the fraction of light absorbed per layer is
10% of the incident flux, then for 100 photons incident on the first layer, AI=0.1 x
100 or 10 will be absorbed and 90 transmitted to the second layer.
NOTES
The light intensity incident on the second layer is (1-A)I and A(1-A)I will be
absorbed on the second layer. The amount transmitted through the second layer is
(1-A)2I. To continue our example, with 90 photons incident on the second layer, A
x 90 = 0.1 x 90 = 9 photons will be absorbed and 81 transmitted. That is:
Layer 1, I photons incident, AI = 0.1x100 = 10 absorbed and
(1-A) I = (1-.1)100 = 90 transmitted
Layer 2, (1-A)I = 90 photons incident, A(1-A)I = 0.1(0.9)100 = 9 absorbed

and
(1-A) (1-A) I = (0.9) (0.9) 100 = 81 are transmitted.

The process continues with fewer photons being transmitted into layer 3,
layer 4, and so on, with fewer photons being absorbed in each successive layer
although the fraction absorbed A remains constant.
The absorption of photons is given in more general form in Table 1 for an

absorbed fraction A.
Table 4.1 Transmission for Absorbed Fraction A
For n layers, the total absorption TA in all layers absorbed fraction A will be
...(6)
The first time in Equation (1) represents the absorption by the first layer. The
second term represents the absorption by the second layer, and so forth.
The total transmitted light TT though n layer is
TT = (1 - A)2 ...(7)
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Equation 1 is more conveniently written using an exponential function. Using an Photophysical Processes
absorption coefficient alpha, the intensity of light at depth t, I(t) for an incident
intensity I0 is given by 8
NOTES
where alpha is given as a fraction per distance such as 0.2 per cm. Figure 4.3
shows the intensity of light as a function of penetration distance into materials with
two different absorption coefficients. The exponential decrease is illustrated on a
linear scale by the curves in Figure 4.3. An increase in alpha leads to a decrease in
penetration. At the depth where the product alpha t equals unity, the intensity has
dropped 1/e of a factor of 0.37 times the incident intensity.
Fig.4.3 Intensity of Light Transmitted Through an Absorbing Material
The above figure shows the intensity of light transmitted through an absorbing
material as a function of thickness d in cm for (1) 10% absorbance and (2) 50%
absorbance per cm. (from T. B. Brill, Light (Plenum Press, New York, 1980))
The relations rely on the fact that the fraction of light which is absorbed is independent
of the intensity of the incident light. For a given wavelength of light, each successive
equi-thickness of the medium absorbs an equal fraction of light passing through it,
but the amount of light it receives is successively decreasing. Hence, the intensity
of light passing though a medium will decrease with depth. The exponential
attenuation coefficients apply for x-rays as well as photons in the visible portion of
the electromagnetic spectrum. The exponential relation is derived in the following:
The number of deltaI of photons which are absorbed in a given thickness deltax is
proportional to the incident intensity I or the number I incident on it:
...(9)
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Photophysical Processes If we use the symbol alpha to denote the absorption coefficient where alpha is the
fraction of photons absorbed per unit thickness, then Equation 10 can be written:
...(10)
or in standard differential notation as:
NOTES
...(11)
This equation can be integrated from the surface at X=0 to a depth x, and leads to
the relation that the intensity I(x) at depth x is given by
...(12)
where I0 is the number of photons at x=0, I0=I(x=0).
The absorption coefficient is a number per unit distance, such as 0.1 per cm which
can be written 0.1 cm-1. At a depth x where alpha x equals unity (in this example,
x=10 cm as 0.1 x 10 =1) the number of photons decreases by a factor of 1/e or
0.37 (the value of e=2.718).
For small values of alpha x, for example alpha x =0.01, Equation 12 can be written
as a linear expansion:
...(13)
This ties into the presentation of the format in Table 4.1.

For x-rays, photoelectric absorption (where the x-ray gives up its energy in a
single interaction with an electron) is the major cause of attenuation of the photons
penetrating the material.
The intensity I of x-rays transmitted through a thin foil of material for an incident
intensity I0follows the exponential attenuation relation of equation 3 with a change
in the nomenclature from alpha to mu to follow the convention of in standard x-ray
usage:
...(14)
where rho is the density of the element (g/cm3), mu is the linear attenuation
coefficient, and mu/rho is the mass attenuation coefficient given in cm2/g. Note that
x-ray absorption is not influenced by the crystal structure of the pigment, but only
by the number of atoms/cm3 and the thickness of the pigment layer.
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NOTES
Fig. 4.4. The x-ray Mass Absorption Coefficient (mu/rho) in cm2/gram

versus x-ray Energy
The above figure shows the x-ray mass absorption coefficient (mu/rho) in cm2/
gram versus x-ray energy in kiloelectron volts (keV) for carbon (C), aluminum
(Al), and tin (Sn). The sharp increase in absorption for Sn at 29.2 keV corresponds
in energy to the K-shell, 1s binding energy (taken from Feldman and
Mayer, Fundamentals of Surface and Thin Film Analysis, (North Halland, New
York. 1986))
Table 4.2 gives the density and mass absorption coefficient at two
wavelengths of several elements found in artists pigments. One notes from the
table, that the mass absorption coefficient tends to increase with increase in atomic
number (Z) and that the absorption coefficient is greater (in some cases a factor of
ten greater) for the longer wavelength (lower energy) photons. There are apparent
anomalies with the absorption of Cd at 0.711Å less than that of arsenic. This is
due to the electronic structure and binding energies of electrons. Figure 4.4 gives
the mass attenuation coefficient as a function of energy for several elements. This
shows both the strong energy dependence of the absorption coefficient (mu/rho
decreases with increasing energy) and the five to ten fold jumps in absorption at
specific energies. These jumps occur when the energy of the photon exceeds the
binding energy of the electrons.
Table 4.2 Atomic Number (Z) Element Density, rho in gm/cm3 and Mass
Attenuation Coefficient in cm2/gm at Wavelengths of 0.711 and 1.54 Å
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NOTES

When a photon of light hits an atom three things can happen: it can bounce off; it
can pass through as if nothing had happened; or it be absorbed. Which one happens
depends on the energy of the light, and which atom it is hitting. Hydrogen will
absorb different energies from helium.
The interesting thing is that each atom will only absorb photons
with exactly the right energy. When the light hits the atom, the atom will only absorb
it if it can use it to bump an electron up an electron shell.
An oxygen atom, for example, has eight electrons, but these fit into two
different electron shells. The innermost shell can only hold two electrons, so the
other six go into the second shell (which can take a maximum of 8). This is the
‘ground state’ of the atom, because it takes the least amount of energy to keep the
electrons in place.
Fig. 4.5 An Oxygen Atom with Two Electrons in the Innermost Shell
and Six in the Second Shell
However, if the atom gets hit by just enough energy, one of the electrons can be
bumped up into a higher shell. The atom will be ‘excited’ and ‘want’ the electron
to drop back down to the lower shell.
And when the electron drops back, it will release the exact same amount of
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80 Material
NOTES
Fig. 4.6 Energy Level/Shell of Hydrogen Atom’s Electron

The above figure shows a hydrogen atom’s electron is bumped up an energy level/
shell by ultraviolet light, but releases that light when the electron drops back down
to its original shell
For hydrogen, the energy to bump up an electron from its first to its second
electron shell comes only from light with a wavelength of 1216 × 10-10m . This is
in the ultraviolet range, which we can not see with the naked eye.
However, the energy absorbed and released when the electron moves
between the second and fourth shells is 6564 × 10-10m, which is in the visible
range. In fact, it’s the red line on the right side of the emission spectrum shown at
the top of the page.
Fig. 4.7 Visible Part of the Emission Spectrum of Hydrogen

The visible part of the emission spectrum of hydrogen and its corresponding electron
shell jumps. Note that different colors of light have different energies, and that the
blue light is more energetic (and has a shorter wavelength) than red light.
Since this emission signature is unique for each element, looking at the colors of
other stars, or the tops of the atmospheres of other planets, is a good way of
identifying the elements in them. You can also do flame tests to identify different
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Material 81
Check Your Progress

1. What is the use of photochemistry?
NOTES 2. In which form is the energy supplied to break the chemical bonds ?
3. Define photochemistry.
4. How does photochemical reactions receive their activation ?
5. What is radiation chemistry?
4.3 PHOTOPHYSICAL PROCESSES OF THE

ELECTRONICALLY EXCITED STATES
Photochemical reaction, a chemical reaction initiated by the absorption of energy in

the form of light. The consequence of molecules’ absorbing light is the creation
of transient excited states whose chemical and physical properties differ greatly
from the original molecules. These new chemical species can fall apart, change to
new structures, ombine with each other or other molecules, or
transfer electrons, hydrogen atoms, protons, or their electronic excitation energy
to other molecules. Excited states are stronger acids and stronger reductants than
the original ground states.
It is this last property that is crucial in the most important of all photochemical
processes, photosynthesis, upon which almost all life on Earth depends. Through
photosynthesis, plants convert the energy of sunlight into stored chemical energy by
forming carbohydrates from atmospheric carbon dioxide and water and releasing
molecular oxygen as a byproduct. Both carbohydrates and oxygen are needed to
sustain animal life. Many other processes in nature are photochemical. The ability
to see the world starts with a photochemical reaction in the eye, in which retinal, a
molecule in the photoreceptor cell rhodopsin, isomerizes (or changes shape) about
a double bond after absorbing light. Vitamin D, essential for
normal bone and teeth development and kidney function, is formed in the skin of
animals after exposure of the chemical 7-dehydrocholesterol to
sunlight. Ozone protects Earth’s surface from intense, deep ultraviolet (UV)
irradiation, which is damaging to DNA and is formed in the stratosphere by a
photochemical dissociation (separation) of molecular oxygen (O2) into individual
oxygen atoms, followed by subsequent reaction of those oxygen atoms with
molecular oxygen to produce ozone (O3). UV radiation that does get through the
ozone layer photochemically damages DNA, which in turn introduces mutations on
its replication that can lead to skin cancer.
Photochemical reactions and the properties of excited states are also critical
in many commercial processes and devices. Photography and xerography are both
based upon photochemical processes, while the manufacture
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of semiconductorchips or the preparation of masks for printing newspapers relies Photophysical Processes
on UV light to destroy molecules in selected regions of polymer masks.

History
The use of photochemistry by humans began in the late Bronze Age by 1500 BCE NOTES
when Canaanite peoples settled the eastern coastline of the Mediterranean. They
prepared a purple fast dye (now called 6,6’-dibromoindigotin) from a
local mollusk, using a photochemical reaction, and its use was later mentioned
in Iron Age documents that described earlier times, such as the epics of Homer and
the Pentateuch. In fact, the word Canaan may mean ‘reddish purple’. This dye,
known as Tyrian purple, was later used to colour the cloaks of the Roman Caesars.
In the simplest photochemical process, excited states can emit light in the
form of fluorescence or phosphorescence. In 1565, while investigating a Mexican
wood that relieved the excruciating pain of urinary stones, Spanish physician Nicolás
Monardes made an aqueous (water-based) extract of the wood, which glowed
blue when exposed to sunlight. In 1853 English physicist George Stokes noticed
that a quinine solution exposed to a lightning flash gave off a brief blue glow, which
he called fluorescence. Stokes realized that lightning gave off energy in the form of
UV light. The quinine molecules absorbed this energy and then re-emitted it as
less-energetic blue radiation. (Tonic water also glows blue because of quinine,
which is added to provide a bitter taste.)
Consequences of Photoexcitation
The chemical nature of a molecule is primarily described by the behaviour of
its electrons. An important facet of quantum mechanics is that the total energy of a
molecule’s electrons (its electronic energy) can take on only certain distinct values;
the energy is said to be quantized. Each distinct energy corresponds to an electronic
state of the molecule. Electronic states are described by a series
of quantum numbers that specify the orbital each electron is in and the intrinsic
spin of each electron. The electron’s spin, which does not literally correspond to
rotation, has only two possible values—referred to as up and down. Each orbital
can contain only one electron of each spin; this is called the Pauli exclusion principle.
If every occupied (or electron-containing) orbital holds a pair of electrons with
opposing spin, the molecule is in a singlet state, which is the pattern for the ground
state of most molecules. When the molecule is excited (for example, by absorption
of a photon), one electron is promoted to a previously unoccupied orbital, and, if
its spin does not change, then the two (now unpaired) electrons still have opposing
spin and the molecule is still in a singlet state. However, occasionally an electron’s
spin will flip when it is excited such that the two unpaired electrons now have
parallel spins and the molecule is in a triplet state. A change in intrinsic electron
spin is not very probable, so conversion of a molecule from singlet to triplet or vice
versa is slow compared with other molecular processes.
The internal energy absorbed from the exciting radiation is lost by either a
radiative transition (fluorescence or phosphorescence) or a non-radiative process.
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Material 83
Photophysical Processes The non-radiative processes are internal conversion, which involves electronic
states of the same electron spin, inter system crossing, which involves states of
different electron spin, or chemistry.
It is worth noting that, in addition to electrons, the behaviour of the nuclei is
NOTES also important in describing the behaviour of the molecule. Motions of the nuclei
relative to each other are usually described as vibrations, and, just as with electronic
energy, the total vibrational energy in a molecule is quantized. However, the
vibrational states of a molecule are spaced much more closely than the electronic
states. Thus, the total energy of a molecule is coarsely defined by its electronic
state and more finely by its vibrational state. Other types of energy with even more
finely spaced states exist but are not discussed here.
Quantum mechanics explains internal conversion as a transfer of excess
electronic energy into excess vibrational energy of a lower electronic state, followed
by dissipation of the vibrational energy into the surroundings as heat. The higher
excited singlet states (S2, S3, and so on, often generally denoted Sn) internally
convert rapidly to S1, the excited state with the lowest energy. Internal conversion
from S1 to S0, the lowest-energy (or ground) state, is much slower, allowing time
for the molecule to either emit a photon (fluorescence), inter-system cross to a triplet
state that rapidly internally converts to T1 (the lowest-energy triplet state), or
undergo a chemical reaction. The T1 level can internally convert to S0, emit a photon
(phosphorescence), or take part in a chemical reaction. This method of accessing
the triplet states (inter-system crossing from S1) is the most common, though they
can also be reached through an extremely weak (that is, improbable) absorption
from the ground state directly to the triplets. Because the unpaired electrons
of triplet states (with parallel spins) interact more strongly than those of singlet
states (with opposing spins), the energy difference T1 – S0 is less than S1 – S0,
and phosphorescence occurs at longer wavelengths than fluorescence. Also, the
low probability of a spin change results in the long-lived nature
of phosphorescence observed by Cellini in 1568 or in glow-in-the-dark products
common today. Because internal conversion is rapid, fluorescence usually occurs
only from S1 (this is called Kasha’s rule), though a small number of molecules are
known that emit from their S2 (azulene) or S3 (pentalene) states.
Both singlet and triplet excited states are distinct in nature and have
completely new properties, including bond length and conformation (molecular
geometry or shape), among others. Because the electrons have a much smaller
mass than the nuclei, absorption of light involves an almost instantaneous change
in the electron configuration, while the nuclei initially remain in their ground-state
positions. Relaxation of the nuclei toward their new excited-state positions lowers
the total energy. This relaxation, called the Stokes shift, is why fluorescence emits
with a lower energy than the original absorption. It is notable that this relaxation
occurs within a single electronic state and so applies when both the absorption
and fluorescence involve the S1 and S0 states.
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84 Material
The quantum yield of luminescence, either fluorescence or phosphorescence, Photophysical Processes
is the fraction of the absorbed radiation that appears as that luminescence. Quantum
yields are less than 100 percent owing to non-radiative processes (for example,
internal conversion) that dissipate the excess internal energy acquired from the
absorbed photon. This energy appears as heat. NOTES
All these events take place over a wide variety of times, most of which are
extraordinarily fast by human standards. Internal conversion and transfer of excess
vibrational energy to the surroundings occur in 30–300 femtoseconds (fs; 1 fs is
10–15 second). The S1 state typically exists for 1–100 nanoseconds (ns; 1 ns is
10–9 second), but if photochemistry occurs, it can exist for less than 100 fs. Inter-
system crossing (from S1 to Tn) occurs in 100 picoseconds (ps; 1 ps is 10–12
second) to 100 ns. The T1 state, in contrast, radiates in 1 millisecond (ms; 1 ms is
1/1,000 second) to 10 seconds, or even longer in extreme cases.
All photochemical processes can broadly be classified into two types: (1) The
primary process and (2) The secondary process.
1. The Primary Process: As a first step, a photochemical reaction requires
absorption of energy. The molecule is thus raised to a higher energy level.
This can lead to four different types of behaviour as shown in figure 4.8. In
type I, transition is from a stable-ground state to a stable excited state. The
corresponding spectrum consists of discontinuous bands with a fine structure
of closely packed lines as shown. Type II represents a transition to an
unstable state which immediately undergoes dissociation. Type III also leads
to dissociation because the energy level reached lies above the binding
energy of the molecule. Type IV is a combination of Type II and Type III.
The initial transition is from one stable state to another but, the upper state
is intersected by the potential energy surface of an unstable state. When the
molecule is vibrating in the excited state, as soon as it reaches a point where
the two curves cross, it undergoes dissociation. This type of behaviour is
referred to as predissociation.
2. The Secondary Process: This process involves the excited atoms,
molecules or free radicals. A large number of paths are available to a
molecule, some of them may lead to the return of the molecule to the ground
state by emission of excess energy while the others produce chemical
decomposition.
Check Your Progress

6. Define photochemical reaction.
7. What are excited states?
8. Where are photochemical reactions used?
9. How many types of photochemical reactions are there?
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Material 85
4.4 FLUORESCENCE AND PHOSPHORESCENCE
Luminescence the emission of radiation from excited species is one of the several
paths by which the excess energy may be lost as shown in Figure 4.8. The general
NOTES
phenomenon of light emission from electronically excited species is known as
luminescence. Luminescent emission provides some of the most reliable information
about the nature of primary photochemical processes. Competition exists between
emission and other factors of excited species (quenching, reaction, decomposition,
etc.) and the dependence of emission intensity on temperature, reactant
concentrations and so on, may yield valuable information about nature and
efficiencies of various processes.
Fig. 4.8 Several routes to loss of electronic excitation

The various individual luminescent phenomena are named according to the
mode of excitation of the energy rich species. We are concerned primarily with
excitation by absorption of radiation and emission from species excited in this way
is referred to as fluorescence or phosphorescence.
Fluorescence
An electronically excited atom must lose its energy by emission of radiation or by
collisional deactivation chemical decomposition is not possible, and radiationless
degradation is extremely improbable. At low enough pressures, therefore,
fluorescent emission is expected from all atoms. Many molecular species who
either, do not exhibit fluorescence or fluoresce weakly even when bimolecular
reaction or physical deactivation does not occur. Some general principles can
suggest whether a polyatomic organic molecule is likely to be strongly fluorescent.
First absorption must occur at a wavelength long enough to ensure that chemical
dissociation does not take place. Absorption to an unstable state is clearly very
unlikely to result in fluorescence. Secondly, intramolecular energy transfer must be
relatively slow compared to the rate of radiation.
In the excited state the molecule is subjected to collision with the environment,
i.e., solvent molecules. Its thermal energy is discarded as thermal motion of the
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86 Material
surroundings. The collisions succeed on lowering the molecule down the ladder Photophysical Processes
of vibrational energy levels, but they may be made to withdraw the larger electronic
energy difference and quench the electronic excitation energy. The molecules might
therefore live long enough to undergo a spontaneous emission and to emit the
excess energy as radiation as it drops to the lower electronic state. The downward NOTES
step occurs vertically in accord with the Franck Condone principle and a series
of lines appear as the fluorescence spectra Figure 4.10. The vibrational structure
of the spectrum is characteristic of the lower electronic state of the system and the
fluorescence spectra provides a valuable method of studying the vibrational
characteristic of the ground state. This mechanism accounts for the observations
that fluorescence radiation has a lower frequency than the incident radiation, the
fluorescence occurs after some energy has been absorbed into the solvent. This
mechanism suggests that the intensity of fluorescence should depend on the ability
of the solvent to withdraw the larger quantum of energy required to lower the
molecule from one electronic state to the other. It has been observed that
fluorescence can be eliminated by selecting a different solvent. For example a
solvent with widely spaced vibrational energy levels (such as water) may be able
to accept the large quantum of electronic energy but one with more closely spaced
levels (such as heavy flabby SeOCl2) night not.
The explanation of fluorescence and phosphorescence can be best understood
from a study of Figure 4.10 this represents the one-electron excitation process.
The absorption of light hvA by the groundstate molecule leads to promotion of one
electron from a ground state MO. to one of the vibrational sublevels of the excited
state MO.,S1 (or to some higher electronic excited, state S2, S3, etc.) This rapidly
deactivates in solution, by a radiationless process to the lowest vibrational sublevel
of S1.
For the electron to return from S1 to the ground state, it must emit radiation
(hvA) which is clearly of lower energy and thus of longer wavelength than hvA the
fluorescent radiation corresponds to hvF.
An alternative path involves loss of energy from S1 to T1, the principle difference
between S1 and T1 is electron spin orientation.
The two electrons originally occupying the ground state MO under
consideration, their must be antiparallel from the Pauli’s exclusion principle. The
excitation followed spins by the decay to the lowest vibrational level of S1 does
not alter the spin of the promoted electron, but the transition S1 to T1 does. Energy
states containing only spin paired electrons are called singlet states (S0,S1,S2) and
those energy states containing parallel spin electrons are called trip lot states (T1...),
etc. Triplet states are more stable than singlet states and are longer lived, as they
survive after the exciting radiation has been removed. These then decay to S0 and
in doing so emit radiation hvP, called phosphorescent radiation. This has been
explained in Figure 4.9.
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Material 87
NOTES
Fig. 4.9 The Sequence of Steps Leading to Fluorescence

Important uses of fluorescence phenomenon are represented by the molecules
of fluorescein and the optical ‘brightener’ derivative of 4,4-diaminostilbene.
The intense green fluorescence of aqueous fluorescein in solutions makes it

an excellent material to add to water systems for leak detection, an excellent
‘maker’ for sea rescue operations etc. Minute quantities of optical brighteners
are added to detergents and are retained on the fabrics after washing in sunlight
they fluoresce blue and add brightness to the fabrics after washing. Other
applications of fluorescence depend on its extremely low detection limit, it is
used in polymer chemistry to detect and identify plasticisers, and in the study of
impurities. Fluorescent material dissolved in solution or in solid plastic bases can
also detect radioactive decay, this forms the basis of scintillation counting of -
emitters, etc. The three dimensional structure of proteins can be studied by measuring
the proximity of known fluorescent group within the protein, these fluorescent
groups can be aromatic amino acids.
In addition to this fluorescence finds wider applications in testing the conditions
of food stuffs, for detecting ring worm. Fluorescent tubes are used for lighting
purposes. The great importance of photochemistry as a branch of science lies
principally in the fact that it provides the chemical potential which is necessary for
biological chemistry to operate. From its earliest abiological stages, the chemical
origin of life were almost certainly photochemical reactions and the food and fuel
of life today is provided by photosynthesis. The discovery of laser has further
Self-Instructional helped in the growth of photochemistry.
88 Material
Phosphorescence: The phenomenon of phosphorescence is similar to fluorescenie Photophysical Processes
with some difference. Figure 4.10 depicts the phenomenon of phosphorescence.

The first steps are the same as in fluorescence but the presence of a second excited
state of the molecule play a decisive role and is present only in phosphorecence.
The second excited state is called the tripled state. It differs from the first state NOTES
(single state) in that in a tripled state spins of two of its electrons are paralled
where as in the singlet state the spins are opposed.
Fig. 4.10 Phosphoresence

At a point indicated in the Figure 4.10 the excited state curves cross the two
states have the same geometry. This singlet or triplet switching is known as inter
system crossing. In most systems this singlet to triplet state crossing is forbidden
while in some other systems it is weakly allowed. This happens in case of the
molecules which contain a heavy atom because its strong spin-orbit interaction
molecules which contain a heavy atom because its strong spin-orbit interaction
can reverse the relative orientations of pairs of electrons.
When a molecule crosses over into the triplet it continues to deposit the energy
into the environment and as it drops down the triplet ladder of vibrational energies.
The ladder terminates at the ground vibrational state of the excited triplet. The
energy of the molecule thus gets trapped. The solvent can not extract the final
large quantum of electronic excitation energy and the molecule can not radiate the
energy because a return to the ground state involves a forbidden singlet triplet
transition. The radiative transition is not completely forbidden, because the spin-
orbit coupling is present and breaks the selection-rule. The molecules are therefore
able to emit slowly and the emission may last long after the original excited state is
formed.
The mechanism explains experimental observation that the energy seems to
be trapped in a slowly leaking reservoir. It also suggests that phosphorescence
should be most intense in solid sample. This is due to the fact that the environment
then colloides less effectively with the molecule and intersystem crossing step
has time to occur as the singlet excited state slowly loss vibrational energy and
falls past the intersection point. The above mechanism also suggests that the
amount of phosphorescence depends on the presence of a heavy atom and due
to the presence of unpaired electrons the excited reservoir state should be magnetic. Self-Instructional
Material 89
Photophysical Processes This has been experimentally confirmed by observance of magnetism in
phosphorescent excited molecules. The common examples of phosphorescent
substances are fluorescein (I), 1-hydroxy-2 naphthoic acid (I) and triphenylene
(III) in boric acid.
NOTES
Lasers: Both fluorescence and phosphorescence are modes of return to the

ground state by spontaneous emission. Laser action, as the aronym laser (light
amplification by stimulated emission of radiation) suggests, depends on emission
by stimulated processes.
A typical laser arrangement is shown in Figure 4.11. By some means a majority
of molecules in the ample are excited into the upper state. For example, a chemical
reaction be used to prepare the species in that state. The sample is contained in a
cavity between two mirrors, and when a molecule emits spontancously the photon,
it generates ricochets backwards and forwards. Its pressure stimulates other
molecules to emit. They add more photons of the same frequency to the cavity,
and these photons stimulate more molecules to emit. The cascade of energy builds
up very rapidly and if one of the mirrors is half-silvered the radiation may be
tapped.
Fig. 4.11 Laser Action by Emission Radiation

The characteristics of laser radiation follow from its manner of generation. It
is monochromatic (because photons travelling at angles to the cavity axis are not
tapped and do not stimulate others).
Fig. 4.12 Laser action by inverting a ground state population

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90 Material
In practice it is often more convenient to use the three-level system shown in Photophysical Processes
Figure 4.12. This is because inverting a ground state population (getting majority
molecules into excited states) is often impossible, but it is often easier to obtain a
relative excess in the upper of two excited states. A typical arrangement would be
to use a powerful source to stimulate the transitions between the first and third NOTES
level (for example, a Xenon lamp, or another laser), this is called pumping and
then to observe laser action to the middle, unpopulated level. The pumping can be
done either with a powerful optical flash as in the ruby laser, or chemically, as in
the chemical laser.
H + F2  2HF*
HF*  HF + photon
Another method depends on a collision of the laser molecule with a species
excited by a radio frequency discharge. This is used in the He–Ne laser, where
some of the neon excited energies just match those in the helium atom; excitation
of neon, followed by collisions with helium atoms, can therefore lead to excited
states when the energy is transferred.
Fig. 4.13 Laser Action by Collision

Solar Energy Conversion: The need to find a substitute for dwindling reserves
of fossil fuels is becoming increasingly apparent. The power from nuclear emission
is becoming unpopular because of the anxieties about the control of reactors and
protection of their waste products. Nuclear power offers the prospects of almost
unlimited energy supply if the formidable technical difficulties can be overcome.
Although tidal and geothermal energy could become locally important they cannot
make a major contribution to global demands. By contrast solar energy is available
everywhere and the total supply for outstrips human’s requirements as the radiant
energy reaching the earth’s surface in one hour approximates to the global
requirements for one year. At noon 1 m2 of the Sahara Desert receives about
1kW of solar power. The efficiency with which the incident radiation can be
converted into usable power will be one of the man factors determining the
exploitation of solar energy where C6H12O6 stands for the basic synthesis product
of the reaction which has glucose structure. The combustion reaction,
complementary to the above process, can be written:
C6H12O6 + 6O2  6CO2 + 6H2O
S = 43.6 cal. deg.–1 mole–1
Gº = – 686 kcal. mole–1
Hº = – 673 kcal. mole–1
Self-Instructional
Material 91
Check Your Progress

10. What is luminescence?
NOTES 11. What does luminescence emission provides?
12. How are various individual luminescent phenomena named ?
13. How can an electron return from S1 to the ground state?

QUESTIONS
1. The importance of photochemistry as a branch of science lies principally in
the fact that it provides the chemical potential which is necessary for biological
chemistry to operate.
2. The energy required to break the chemical bonds involved in the reaction,
is usually supplied in the form of thermal energy. However, other forms of
energy, such as light and sound, have also been used to initiate chemical
reactions.
3. The branch of chemistry which deals with the study of chemical reactions
produced directly or indirectly by light is called photochemistry.
4. Photochemical reactions receive their activation by the absorption of photons
of light molecules.
5. Radiation chemistry comprises the study of chemical effects produced by
ionizing radiations.
6. Photochemical reaction, a chemical reaction initiated by the absorption
of energy in the form of light.
7. Excited states are stronger acids and stronger reductants than the
8. Photochemical reactions and the properties of excited states are also critical
in many commercial processes and devices. Photog-
raphy and xerography are both based upon photochemical processes, while
the manufacture of semiconductorchips or the preparation of masks for
printing newspapers relies on UV light to destroy molecules in selected
regions of polymer masks.
9. All photochemical processes can broadly be classified into two types:
 Primary process
 Secondary process
10. Luminescence the emission of radiation from excited species is one of the
several paths by which the excess energy may be lost.
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92 Material
11. Luminescent emission provides some of the most reliable information about Photophysical Processes
the nature of primary photochemical processes.

12. The various individual luminescent phenomena are named according to the
mode of excitation of the energy rich species. We are concerned primarily
with excitation by absorption of radiation and emission from species excited NOTES
in this way is referred to as fluorescence or phosphorescence.
13. For the electron to return from S1 to the ground state, it must emit radiation
(hvA) which is clearly of lower energy and thus of longer wavelength than
hvA the fluorescent radiation corresponds to hvF.
4.6 SUMMARY
 The importance of photochemistry as a branch of science lies principally in

the fact that it provides the chemical potential which is necessary for biological
chemistry to operate. From its earliest biological stages, the chemical origins
of life were almost certainly photochemical reactions and the food and fuel
of life, today is provided by photosynthesis.
 The discovery of laser has further helped in the growth of photochemistry.
Earlier we have seen that in order to initiate a chemical reaction, the reactant
molecules must overcome an energy barrier.
 The energy required to break the chemical bonds involved in the reaction,
is usually supplied in the form of thermal energy. However, other forms of
energy, such as light and sound, have also been used to initiate chemical
reactions.
 The branch of chemistry which deals with the study of chemical reactions
produced directly or indirectly by light is called photochemistry.
 Photochemical reactions receive their activation by the absorption of photons
of light molecules.
 Radiation chemistry comprises the study of chemical effects produced by
ionizing radiations.
 The fraction of the incident light absorbed by a homogeneous medium
depends on the depth or the thickness of the medium. This is known as
Lambert’s law which states that when a beam of monochromatic radiation
passes through a homogeneous absorbing medium, equal fractions of the
incident radiation are absorbed by successive layers of equal thickness of
the light absorbing substance.
 The Beer’s law is valid only in dilute solution and when monochromatic light
is used. The extinction coefficient e varies a great deal from substance to
substance and also with the wavelength of the light used. The nature and
position of the absorption band determines the colour of the substance.
Self-Instructional
Material 93
Photophysical Processes  The formalism for the absorption of light in the simplest case starts with a
beam of light of intensity I of photons that has just penetrated into a material
with a uniform concentration of absorbing pigments.
 The mechanism for absorption is that a photon transfers all its energy to an
NOTES
electron in the absorbing material. The photon is ‘lost’ from the light beam
as it is absorbed in a single event.
 The electron is excited by the gain in energy to a higher energy state in the
electron configuration around the atom. This single-event transfer of photon
energy to an electron and the disappearance of the photon is closely related
to the photoelectric effect where the electron is ejected from the material in
a single event.
 The decrease in intensity of the light or photon flux as the beam penetrates
into the material can be visualized if we separate the absorbing material into
a set of thin, equal thickness slices of thickness t.
 When a photon of light hits an atom three things can happen: it can bounce
off; it can pass through as if nothing had happened; or it be absorbed.
Which one happens depends on the energy of the light, and which atom it is
hitting. Hydrogen will absorb different energies from helium.
 An oxygen atom, for example, has eight electrons, but these fit into two
different electron shells. The innermost shell can only hold two electrons, so
the other six go into the second shell (which can take a maximum of 8). This
is the ‘ground state’ of the atom, because it takes the least amount of energy
to keep the electrons in place.
 The visible part of the emission spectrum of hydrogen and its corresponding
electron shell jumps. Note that different colors of light have different energies,
and that the blue light is more energetic (and has a shorter wavelength) than
red light.
 Vitamin D, essential for normal bone and teeth development and kidney
function, is formed in the skin of animals after exposure of the chemical 7-
dehydrocholesterol to sunlight.
 Ozone protects Earth’s surface from intense, deep ultraviolet (UV)
irradiation, which is damaging to DNA and is formed in the stratosphere by
a photochemical dissociation (separation) of molecular oxygen (O2) into
individual oxygen atoms, followed by subsequent reaction of those oxygen
atoms with molecular oxygen to produce ozone (O3).
 UV radiation that does get through the ozone layer photochemically damages
DNA, which in turn introduces mutations on its replication that can lead
to skin cancer.
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94 Material
 Photochemical reactions and the properties of excited states are also critical Photophysical Processes
in many commercial processes and devices.

 Photography and xerography are both based upon photochemical
processes, while the manufacture of semiconductorchips or the preparation
NOTES
of masks for printing newspapers relies on UV light to destroy molecules in
selected regions of polymer masks.
 Luminescence the emission of radiation from excited species is one of the
several paths by which the excess energy may be lost. The general
phenomenon of light emission from electronically excited species is known
as luminescence.
 An electronically excited atom must lose its energy by emission of radiation
or by collisional deactivation chemical decomposition is not possible, and
radiationless degradation is extremely improbable. At low enough pressures,
therefore, fluorescent emission is expected from all atoms.
 Absorption to an unstable state is clearly very unlikely to result in
fluorescence. Secondly, intramolecular energy transfer must be relatively
slow compared to the rate of radiation.
 The collisions succeed on lowering the molecule down the ladder of
vibrational energy levels, but they may be made to withdraw the larger
electronic energy difference and quench the electronic excitation energy.
 It has been observed that fluorescence can be eliminated by selecting a
different solvent. For example a solvent with widely spaced vibrational
energy levels (such as water) may be able to accept the large quantum of
electronic energy but one with more closely spaced levels (such as heavy
flabby SeOCl2) night not.
4.7 KEY WORDS
 Photochemistry: The branch of chemistry which deals with the study of

chemical reactions produced directly or indirectly by light is called
photochemistry.
 Radiation chemistry: Radiation chemistry comprises the study of chemical
effects produced by ionizing radiations.
 Photochemical reaction: Photochemical reaction, a chemical
reaction initiated by the absorption of energy in the form of light.
 Luminescence: Luminescence is the emission of radiation from excited
species is one of the several paths by which the excess energy may be lost.
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Material 95
EXERCISES
NOTES Short Answer Questions

1. What is absorption of light?
2. Brief a note on mechanism of absorption of light.
3. Write short note on absorption of light in atoms.
4. What is a photochemical reaction ?
5. Brief a note on consequences of photo-excitation.
6. Write a short note on fluorescence.
1. Explain in detail about the absorption of light and its process.
2. Discuss about the mechanism of absorption of light and absorption of light
in atoms. Also give the well labelled diagram.
3. Elaborate a note on photochemical reaction, its history and consequences
of photo-excitation.
4. Explain the types of photochemical processes in detail.
5. Write an elaborated note on fluorescence explaining with the help of diagrams.
6. Give a detailed note on phosphorescence and explain it with the help of
relevant diagrams.

& Company Ltd.
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96 Material
Energy Transfer
UNIT 5 ENERGY TRANSFER Mechanisms
MECHANISMS
NOTES
Structure
5.0 Introduction
5.1 Objectives
5.2 Energy Transfer Mechanisms
5.3 Photosensitization and Chemiluminescence
5.4 Actinometers
5.5 Quantum Yield Determination
5.7 Summary
5.8 Key Words
5.0 INTRODUCTION
Energy transfer refers to a process in which an excited atom or molecule (donor)

transfers its excitation energy to an acceptor atom or molecule during the lifetime
of the donor excited state. If the acceptor is a luminescent species, it can emit by
virtue of energy transfer, i.e., the acceptor luminesces as a result of the excitation
of the donor. Such a luminescence is called ‘sensitized luminescence’, and some
textbooks use the terms ‘sensitizer’ and ‘activator’ instead of ‘donor’ and
‘acceptor’. Many applications in chemistry, physics, materials science and
biochemistry are based on sensitized luminescence. A later section provides an
example of the application of energy transfer processes in biological systems. Energy
transfer processes occur via radiative or non-radiative mechanisms.
Photochemistry refers to the study of those specific chemical reactions which
result after the distinctive exposure of light radiations. Principally, the light provides
the essential energy that is required by the photochemical reactions to take place.
In photochemical reactions, the visible and UV radiations of 2000-8000Å
wavelength are generally used.
In this unit, you will study about the energy transfer mechanisms,
photosensitization and chemiluminescence, actinometers and quantum yield
determination.
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Material 97
Energy Transfer
Mechanisms 5.1 OBJECTIVES

NOTES  Understand the energy transfer mechanisms
 Discuss photosensitization and chemiluminescence
 Explain what actinometers are
 Discuss the quantum yield determination
5.2 ENERGY TRANSFER MECHANISMS
Energy transfer refers to a process in which an excited atom or molecule (donor)

transfers its excitation energy to an acceptor atom or molecule during the lifetime
of the donor excited state. Figure 5.1 shows that as a result of energy transfer, the
donor returns to its ground state while the acceptor is promoted to its excited
state. If the acceptor is a luminescent species, it can emit by virtue of energy
transfer, i.e., the acceptor luminesces as a result of the excitation of the donor.
Such a luminescence is called ‘sensitized luminescence’, and some places it is also
used as ‘sensitizer’ and ‘activator’ instead of ‘donor’ and ‘acceptor’. Many
applications in chemistry, physics, materials science and biochemistry are based
on sensitized luminescence. A later section provides an example of the application
of energy transfer processes in biological systems. Energy transfer processes occur
via radiative or non-radiative mechanisms.
Fig. 5.1 Energy Transfer from a Donor (D) to an Acceptor (A).
Radiative Mechanisms
This mechanism involves the absorption of light by a donor atom or molecule (D)
followed by emission of a photon by the donor and the absorption of the emitted
photon by another molecule called the acceptor (A). The process can be
represented as follows:
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98 Material
Energy Transfer
Mechanisms
NOTES
The radiative mechanism is important if the acceptor A absorbs at the wavelength

at which the donor emits. The efficiency of the process is determined simply by the
quantum yield of the donor luminescence and the absorbance of the acceptor at
the donor emission wavelength. No significant interaction between A and D is
required in this mechanism and, therefore, radiative energy transfer can occur over
extremely large separations of D and A. The radiative mechanism is not important
if A and D are similar molecules because of the usually small overlap of the emission
and absorption spectra in this case.
Non-Radiative Mechanisms
The radiative mechanism is a trivial case of energy transfer because it can be
characterized by measuring the donor absorption and the acceptor emission
separately from each other. In fact, most textbooks refer to the radiative pathway
as a ‘trivial mechanism’ for energy transfer and do not really consider it as an energy
transfermechanism. In Figure 5.1 the donor does not emit light. Instead, the
excitation energy is transferred non-radiatively to the acceptor. The non-radiative
pathway shown in Figure 5.1 is the mechanism that is typically used in most
textbooks to represent energy transfer processes. Non-radiative energy
transfer processes occur via two major mechanisms, the Förster resonance
mechanismand the Dexter exchange mechanism.
The Förster resonance mechanism involves an electrostatic interaction
between D and A. Such an interaction can occur over a long range, i.e., it does not
require a very short contact between the donor and the acceptor. Energy transfer via
the resonance mechanism may proceed over donor–acceptor distances as long as
50–100 Å. In order for energy transfer to be efficient via the resonance mechanism,
the energies of the donor and acceptor transitions D* D and A ’ A* must be
nearly identical (hence the name ‘resonance mechanism’). Nevertheless, the
presence of phonons (vibrational quanta) may provide assistance for energy
transfer when small differences exist between the donor and acceptor excited states.
Such processes are called phonon-assisted energy transfer processes (Refer Figure
5.2). The energies of the phonons should be high enough to surmount the difference
between the donor and acceptor excited states. However, too high phonon energies
increase the likelihood of non-radiative de-excitation, which would take place
before energy transfer can take place.
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Material 99
Energy Transfer
Mechanisms
NOTES
Fig. 5.2 Phonon-Assisted Energy Transfer

The above Figure 5.2 shows the phonon-assisted energy transfer. The energy
difference between the excited states of D and A is provided by phonons
The Dexter Exchange Mechanism involves a direct contact between the
donor and the acceptor atoms or molecules. The exchange interaction between
the donor D and acceptor A involves a transition state with a D–A distance that is
close to the sum of the gas-kinetic collision radii of D and A, respectively. Therefore,
information about the energy transfer mechanism can be gained by structural studies
of the system under consideration. If the D–A distance is short (normally < 5 Å)
then the exchange mechanism is the more likely, but if the D–A distance is long
(>> 5 Å) then the resonance mechanism would be more likely.
The energy transfer efficiency is strongly dependent on the spectral overlap
between the donor emission and the acceptor absorption. This is valid for both
exchange and resonance mechanisms, as shown in the following expression for
the energy transfer rate:
where the integral represents the spectral overlap between the donor
emission ID and the acceptor absorption å A. The factor f(rD–A) is a function of
the inter molecular distance between the donor and acceptor centres (rD–A) and
is governed by the relevant energy transfer mechanism (Förster or Dexter
mechanism). The donor–acceptor spectral overlap can be determined
experimentally by spectroscopic measurements, as illustrated in Figure 5.3.
Fig. 5.3 Experimental Determination of the Donor–Acceptor Spectral Overlap from

Self-Instructional Emission and Absorption Spectra.
100 Material
When a molecule is electronically excited the total energy of the molecule may be Energy Transfer
Mechanisms
written as
Etotal = E electronic +E vibrational +E rotational
A change in the total energy of the molecule may be written as NOTES
E total = Eele + Evib + Erot.
or  total = ele + vib + rot.
The approximate orders of magnitudes of these changes are
ele  vib × 103  rot. × 106
Franck-Condon principle states that an electronic transition takes place so
rapidly that a vibrating molecule does not change its internuclear distance during
the transition.
If a diatomic molecule undergoes a transition into an upper electronic state
in which excited molecule is stable with respect to dissociation into its atoms.
There are three possibilities in such a case as shown in Figure 5.4.
Fig. 5.4 Illustration of Franck Condon Principles
(i) internuclear distances equal in upper and lower states (ii) upper state inter
nuclear distance is little greater than that in the lower state (iii) upper state
distance is considerably greater.
In (i) we show the upper electronic state having the same equilibrium inter nuclear
distance as the lower. The transition occurs vertically since the inter nuclear
distance does not change. Thus, the strongest line will be (0, 0).
In (ii) a case is shown where the excited electronic state has a slightly higher inter
nuclear separation than the ground state. A vertical transition from v = 0
to v = 2 will most likely occur. (Z,0) transition will thus most intense.
(iii) the upper state separation is drawn as considerably greater than that in the
lower state. The electronically excited molecule is fragmented into two or
more components. The onset of dissociation can be detected by observing Self-Instructional
Material 101
Energy Transfer where the vibrational structure of the molecule ends this is the dissociation
Mechanisms
limit of the spectrum. This helps us in determining the dissociation energy
of the molecule. In some cases however the vibrational structure disappear
as but the molecule returns to higher energies. This behaviour is called
NOTES predissociation and can be interpreted in terms of the molecular energy
curves. When the molecule makes a transition in the vibrational energy
levels in the region when one molecular potential energy curve crosses the
other, there may be reorganisation of its electrons switching from one
state to another. The nuclear geometry at the crossing point of the two
states is the same. This process is called internal conversion. When a molecule
changes to another state in may have enough to dissociate. Hence the
energy levels in the vicinity of the intersection of the curves may have a
unbound character and the vibrational structure of the spectrum blurs into
a continunum. The moment the excitation source supplies energy sufficient
enough to raise the molecule into the dissociative state. The vibrational
structure becomes well defined and the spectrum acquires a fine structure.
Check Your Progress

1. What is radiative mechanism?
2. Why is radiative mechanism a trivial case of energy transfer?
3. How does non-radiative energy transfer processes occur?
4. What does Dexter exchange mechanism involves?
5.3 PHOTOSENSITIZATION AND

CHEMILUMINESCENCE
Photochemistry refers to the study of those specific chemical reactions which

result after the distinctive exposure of light radiations. Principally, the light
provides the essential energy that is required by the photochemical reactions
to take place. In photochemical reactions, the visible and UV radiations of
2000-8000Å wavelength are generally used.
In chemistry, typically in several photochemical reactions the usually the reacting
matter or substance does not directly absorb radiation, however it obtains the
essential energy from some of the other different external substance or matter
which have light absorbing properties. These external substance or matter is
acknowledged as sensitizer. Therefore, when the photosensitized is absent
then no reaction can occur because it is not possible for the reacting substance
Self-Instructional
102 Material
or matter to absorb its own radiation. The chemical process which uses the Energy Transfer
Mechanisms
photosensitizer is termed as photosensitizer reactions.
Definition 1: Photosensitization is referred as the process of initiating a reaction
through the use of a substance capable of absorbing light and transferring the
NOTES
energy to the desired reactants.
Definition 2: Photosensitization is a reaction to light that is mediated by a light-
absorbing molecule, which is not the ultimate target. Photosensitization can involve
reactions within living cells or tissues, or they can occur in pure chemical systems.
The photosensitization technique is generally used in photochemical work,
principally for those reactions which require light sources of certain specified/
definite wavelengths that are not obtainable readily. The mercury is the sensitizer
which is frequently used and it has the potential of absorbing radiation at 1849
and 2537 angstroms; these are distinctive wavelengths of light that are
specifically produced/formed by the mercury lamps of high-intensity. In addition,
the cadmium, and some of the noble gases specifically xenon, zinc,
benzophenone, and several organic dyes are also used as sensitizers.
Various forms of mercury-photosensitized reaction are commonly known and
distinguished. One such example includes the combination mechanism of carbon
monoxide and hydrogen as shown below:
Hg + hv  Hg*
Hg* + H2  Hg + 2H
H + CO  HCO
HCO + H2  HCHO + H
2HCO  HCHO + CO
2HCO  HCOCHO (Glyoxal)
Typically, in a characteristic photosensitized reaction, for example in the mercury
lamp when the photodecomposition process of ethylene to acetylene and
hydrogen occurs then we obtain a mixture of mercury vapour and ethylene
which causes the mercury lamp to illuminate or brighten. In this process the
light energy is absorbed by the mercury atoms such that there is an appropriate
electronic transition in the atom which sequentially corresponds to the energy
of the incident light. When the mercury atoms are collided with the ethylene
molecules, then the mercury atoms transfer the energy and become deactivated
to their initial or original state of energy. These activated or initiated ethylene
molecules then undergo decomposition subsequently.
In addition, in uranyl actinometer the photosensitizer used is uranyl. The most
common and significant example of photosynthesized reactions include the
photosynthesis process of carbohydrates in plants in which the sensitizer is
chlorophyll. The reaction is as follows,
6CO2 + 6H2O  C6H12O6 + 6O2
Self-Instructional
Material 103
Energy Transfer The Mechanism of Photosensitization Reactions
Mechanisms
According to the ‘First Law of Photochemistry’, (The light photons) must be
absorbed to have an effect. It has the following two possible processes:
NOTES Process 1. The molecule that absorbs the photon is itself altered chemically, but it
does not change or alter any other molecule in the system.
Process 2. The molecule that absorbs the photon eventually/ultimately alters another
molecule in the system.
The Process 2 is termed as ‘Photosensitization’ where the molecule that absorbs
the photon is termed as the photosensitizer or simply sensitizer, while the altered
molecule is termed as the acceptor or substrate. For photosensitization to occur
both the photosensitizer and light are essential as shown below.
Photosensitizer  No Effect or Change
Light  No Effect or Change
Photosensitizer and Light  Photosensitization (Change)
The very significant point is that usually during photosensitization reactions the
‘Photosensitizers’ are not consumed or utilized. They return or reoccur to their
original state as soon as the photosensitization reaction is complete.
Significance of Photosensitizer
 A photosensitizer is a molecule that produces a chemical change in another
molecule in a photochemical process.
 Photosensitizers are commonly used in polymer chemistry in reactions, such
as photopolymerization, photocrosslinking, and photodegradation.
 Photosensitizers are also used to generate triplet excited states in organic
molecules with uses in photocatalysis, photon upconversion and
photodynamic therapy.
 Photosensitizers generally act by absorbing ultraviolet or visible region
of electromagnetic radiation and transferring it to adjacent molecules.
 Photosensitizers usually have large de-localized ð systems, which lower the
energy of HOMO orbitals and its absorption of light might be able to ionize
the molecule.
 The semiconductor quantum dots are also used as photosensitizers.
In chemistry, several reactions are accompanied by the emission of light. This
characteristic phenomenon is known as ‘Chemiluminescence’. The product
formed during chemiluminescence follows the standard electronic state and
emit radiation of appropriate wavelength as defined in the visible region of the
Self-Instructional spectrum.
104 Material
The common examples of chemiluminescence include the reactions of Energy Transfer
Mechanisms
phosphorous and its trioxides in air, oxidation reaction by oxygen present in
the air with various Grignard reagents, oxidation of alkaline aqueous solutions
of 5-aminophthalic hydrazide, the light of ‘Firefly’ (light emitted by the
organisms), etc. When chemiluminescence takes place in living organisms, the NOTES
phenomenon is called bioluminescence. A light stick emits light by
chemiluminescence.
Definition: Chemiluminescence, also termed as chemoluminescence, is
the emission of light (luminescence) which occurs as the result of a chemical
reaction.
During chemiluminescence, there may also be limited emission of heat. Given
reactants A and B, with an excitation or motivated intermediate Ê%,
[A] + [B]  []  [Products] + Light
For example, if the reaction for both [A] as luminol and [B] as hydrogen
peroxide takes place in the presence of a suitable catalyst then we have,
Where,
 3-APA is 3-aminophthalate.
 3-APA[] is the vibronic excitation or motivated state fluorescing as it
decays to a lower energy level.
Basically, the decay of the excitation or motivated state[] to a lower energy
level causes light emission.
As per the electronic theory, one photon of light must be given off for each
molecule of reactant. This is equivalent to Avogadro’s number of photons per
mole of reactant. Authentically, non-enzymatic reactions seldom exceed 1%
QC, Quantum Efficiency.
In a chemical reaction, reactants collide to form a transition state, the enthalpic
maximum in a reaction coordinate which gives the product. Normally, reactants
form products of lesser chemical energy. The difference in energy between
reactants and products, represented as rxn is turned into heat, physically
realized as excitations in the vibrational state of the normal modes of the product.
Since vibrational energy is generally much greater than the thermal agitation, it
rapidly disperses in the solvent through molecular rotation. Due to this the
solutions of exothermic reactions become hotter. In a chemiluminescent reaction,
the direct product of the reaction is an excited electronic state. This state then
decays into an electronic ground state and emits light through either an allowed
transition (analogous to fluorescence) or a forbidden transition (analogous to
phosphorescence), depending partly on the spin state of the electronic excited
state formed. Self-Instructional
Material 105
Energy Transfer Chemiluminescence differs from fluorescence or phosphorescence in respect
Mechanisms
that the electronic excited state is the product of a chemical reaction rather
than of the absorption of a photon. It is the antithesis of a photochemical
reaction, in which light is used to drive an endothermic chemical reaction.
NOTES Here, light is generated from a chemically exothermic reaction. If the
chemiluminescence is induced by an electrochemical stimulus, then in this case
it is called electrochemiluminescence.
A standard and common example of chemiluminescence in the laboratory testing
methods is the luminol test. Here, blood is indicated by luminescence upon
contact with iron in hemoglobin.
Liquid Phase Reactions
Chemiluminescence in aqueous system is mainly caused by redox reactions.
Luminol in an alkaline solution with hydrogen peroxide in the presence of iron
or copper, or an auxiliary oxidant, produces chemiluminescence. The luminol
reaction is given by,
Check Your Progress

5. What is photochemistry?
6. What are used in photochemical reactions?
7. Define photosensitization.
8. What is photosensitizer?
5.4 ACTINOMETERS
Actinometers are the devices specifically used for measuring the heating power of
radiation and also used in meteorology for measuring the solar radiation as
pyranometers, pyrheliometers and net radiometers.
Principally, an actinometer is a chemical system or physical device which
determines the number of photons in a beam integrally or per unit time.
The name actinometer is commonly given to devices that are used in the ultraviolet
and visible wavelength ranges. For example, solutions of iron or Fe (III) oxalate
can be used as a chemical actinometer, while bolometers, thermopiles, and
photodiodes are physical devices which provide a reading that can be correlated
to the number of photons detected.
In chemistry, an actinometer is defined as a device that is used to measure the
Self-Instructional intensity of solar radiation. It is a chemical system that determines the number of
106 Material
photons by measuring the rate of change of photoinduced responses in a chemical Energy Transfer
Mechanisms
system.
Figure 5.6 illustrates the actinometer device that is designed by Jules Violle
and is specifically used for estimating the temperature of the surface of the Sun.
NOTES
Fig. 5.6 Actinometer Designed by Jules Violle
The actinometer was first invented by John Herschel (1825) who introduced the
term actinometer. The prefix ‘actin’ in the term ‘actinometer’ means scientific
instruments, effects and processes. The actinograph is other related device that is
used to estimate the actinic power of lighting for photography.
Chemical Actinometry
Chemical actinometry includes measuring radiant flux via the yield from a chemical
reaction. It essentially requires a chemical with a known quantum yield and easily
analyzed reaction products.
Selecting an Actinometer
For analysing the reaction products, we need a proper actinometer. Potassium
ferrioxalate is commonly used, because it is simple to use and sensitive over a
wide range of relevant wavelengths, basically 254 nm to 500 nm. Other actinometers
include malachite green leucocyanides, vanadium (V) – iron (III) oxalate and
monochloroacetic acid, however all of these undergo dark reactions, i.e., they
react in the absence of light. Organic actinometers, such as the butyrophenone or
piperylene are analysed by gas chromatography. Some other actinometers are
more specific in terms of the range of wavelengths at which quantum yields have
been determined. Reinecke’s salt with chemical formula K[Cr(NH3)2(NCS)4]
reacts in the near-UV region although it is thermally unstable. Uranyl oxalate has
been used historically but it is very toxic and cumbersome to analyze.
Self-Instructional
Material 107
Energy Transfer Recent studies on nitrate photolysis have defined the use of 2-nitrobenzaldehyde
Mechanisms
and benzoic acid as a radical scavenger for hydroxyl radicals that is produced in
the photolysis of hydrogen peroxide and sodium nitrate. Though, they originally
used ferrioxalate actinometry to calibrate or regulate the quantum yields for the
NOTES hydrogen peroxide photolysis. Radicals evidenced a feasible method of measuring
production of hydroxyl radical.
Chemical Actinometry in the Visible Range
Meso-diphenylhelianthrene can be used for chemical actinometry in the visible
range, i.e., from 400–700 nm. Though this chemical measures in the 475–610 nm
range, but it can also measure the wider spectral ranges with this chemical if the
emission spectrum of the light source is known.
Working Principle of Chemical Actinometer
In chemistry, the actinometer is considered as a substance or a mixture of substances
that reacts through the action of light. Because the quantitative relationship between
the extent of the reaction and the energy of the absorbed light can be easily
determined, hence it is frequently used as a standard for measurement of light
energies involved in photochemical work.
A typical actinometer is a liquid solution of oxalic acid containing uranyl sulfate.
Light in the wavelength range of about 2,080 to 4,350 angstroms, i.e., ultraviolet
to violet light decomposes the oxalic acid into a mixture of carbon dioxide, carbon
monoxide and water through a complex process involving initial absorption of the
light energy by the uranyl ion. Generally, a standard solution is irradiated with light
of the proper wavelength and of known intensity, and then the quantity of oxalic
acid decomposed is accurately measured by titration with potassium permanganate.
In the experiment, the relationship between the quantity of oxalic acid transformed
and the quantity of light energy absorbed is determined using a scale to predict
either quantity when the other is known or measured. In addition to the oxalic
acid–uranyl sulfate solution, other substances that are normally used as chemical
actinometers include acetone, hydrogen bromide, carbon dioxide and a solution
of ferrioxalate in sulfuric acid.
For an efficient actinometer, this quantum yield has to be independent of oxygen,
trace impurities, temperature and excitation wavelength. The following are the
basic steps employed in the working principle of chemical actinometers:
 The specified gas is filled into a photolysis reactor.
 The actinometer is exposed to heat radiation.
 The photochemical rate is measured.
Basically, the actinometer gas is considerably exposed to actinic flux without
altering the radiation intensity and spectral composition and from the measurement
or reading obtained the photolysis frequency can be easily evaluated.
Self-Instructional
108 Material
During the measurement, the actinometer is uncovered and exposed to heat Energy Transfer
Mechanisms
radiation for a fixed interval of time, then the actinometer is closed again and
analyzed for change in the gas composition. When the gas passes through the
reactor, its composition is analyzed using an online gas detector. Photolysis
frequencies can be continuously monitored in this mode. NOTES
The actinometers are mostly used in meteorology for measuring solar
radiation that is transmitted by the sun, reflected by the earth or scattered by the
atmosphere, in photochemical experiments that involve complex irradiation
geometry, and for calibrating photochemical detectors used for radiation
measurements.
Check Your Progress

9. What are actinometers?
10. What does chemical actinometry includes?
11. Where are actinometers used?
5.5 QUANTUM YIELD DETERMINATION
The law of Photochemical Equivalence

A Einstein in 1912 applied the concept of the quantum of energy to photochemical
reactions of molecules. This law, sometimes is called the law of photochemical
equivalence or the principle of quantum activation states: Each quantum of
radiation absorbed by a molecule activates one molecule in the primary step
of photochemical process.
The energy E absorbed per mole in a photochemical process is given by
E = Nhv ...(1)
where v is the frequency of the absorbed radiation, h is Planck’s constant and
N is the Avogadro’s number. Since v is equal to c/, where c is the velocity of light
and  is the wave length in cm, Equation (1) can not be written as,
Nhc
E= ergs mole–1 ...(2)

Substituting the numerical values for N, h and c we get,
6.025  1023  6.625  1027  2.998  1010
E=

1.196  1016
E= ergs mol–1

2.859
or E= × 105 kcal mol–1 ...(3)

Self-Instructional
Material 109
Energy Transfer The quantity E defined by (2) is called one einstein of radiation of the given
Mechanisms
wavelength . It can be seen from this equation that the energy absorbed per mole
decreases as the wavelength increases. In other words, the value of energy is
inversely proportional to the wavelength of the light absorbed.
NOTES
The Quantum Yield
The law of photochemical equivalence is applicable only to primary photochemical
process, i.e., when as a result of absorption of light, only one molecule decomposes
and the products enter no further reaction. The Einstein law is usually marked by
secondary reactions and radiative and non-radiative transitions which present a
simple 1 : 1 relationship between the number of photon absorbed and the number
of molecules of final products in the reaction. The results of photochemical process
are frequently expressed in terms of the quantum yield or quantum efficiency of
the reaction. It is the number of moles of reactant consumed or product formed
for each einstein of light absorbed. This quantity is defined as
Number of moles reacting
Quantum yield  = ...(4)
Number of einstiens absorbed
An experimental arrangement for a photochemical study is shown in Figure
5.7. The light from the source passes through a monochromotor which yields light
of definite wavelength (). The light from a monochromotor enters a reaction cell
filled with the reaction mixture. The part of light which is not absorbed strikes the
detector, mostly a thermopile. The intensity of light is measured with the empty cell
and with a reaction mixture.
Photoelectric cell can also be used as detectors, but they must be calibrated
for each frequency. Chemical actinometers are often used to measure the intensity
of light radiation. It utilises a chemical reaction which has been accurately
investigated in its photochemical behaviour. One of the most reproducible reactions
is the decomposition of oxalic acid in presence of uranyl sulphate. The reaction
can be written as
UO2 + hv  (UO2++)*
(UO2++)* + (COOH)2  UO++ 2 + CO2 + CO + H2O
The oxalic acid concentration can be determined by titration with permanganate.
This reaction has a quantum yield of 0.50.
Fig. 5.7 Arrangement for Photochemical Studies

Self-Instructional
110 Material
It has been found that the law of photochemical equivalence applies only to the Energy Transfer
Mechanisms
primary process of the reaction since only in a few cases the quantum yield is unity as
required by the law of the photo-chemical equivalence. The values of quantum yields
range from almost zero to very large values, for example, 105.
NOTES
Example 5.1: In the photobromination of cinnamic acid to dibromocinnamic acid,
using light of wavelength 4358 at 30.6º a light intensity of 14,000 ergs sec–1
produced a decrease of 0.075 millimole of bromine during an exposure of 1105
sec. The solution absorbed 80.1 per cent of the light passing through it. Calculate
the quantum yield.
hc
Solution. E = hv =

E = (6.62 × 10–27) (3 × 1010) (4.358 × 10–5)
E = 4.54 × 10–12 erg per quantum
(14.000) (0.801) (1105)
Number of quanta absorbed =
4.54  10 12
= 2.74 × 1016
Number of molecules of Br2 reacting = (7.5 × 10–5) (6.02 × 1023)
= 45.2 × 1018
45.2  108
Quantum efficiency () = = 16.5
2.74  1018
Example 2: From the following data for the uranyl uxalate system, evaluate the
quantum efficiency at each wave length.
Wave length Fraction of Molecules Photons
m oxalate decomposed decomposed × 1018 absorbed × 10–18
365.5 0.0592 5.18 10.58
435.8 0.0242 2.10 3.64
435.8 0.0208 1.79 3.10
Solution. At 365.5 m
number of molecules decomposed
=
number of photons absorbed
5.18 × 1018
= = 0.490
10.58  1018
At 435.8 m
2.10  1018
= = 0.576
3.64  1018
At 435.8 m
1.79  1018
= = 0.577
3.10  1018
Self-Instructional
Material 111
Energy Transfer
Mechanisms 5.6 ANSWERS TO CHECK YOUR PROGRESS
QUESTIONS
NOTES 1. Radiative mechanism involves the absorption of light by a donor atom or

molecule (D) followed by emission of a photon by the donor and the
absorption of the emitted photon by another molecule called the acceptor
(A).
2. The radiative mechanism is a trivial case of energy transfer because it can
be characterized by measuring the donor absorption and the acceptor
emission separately from each other.
3. Non-radiative energy transfer processes occur via two major mechanisms,
the Förster resonance mechanismand the Dexter exchange mechanism.
4. The Dexter Exchange Mechanism involves a direct contact between the
donor and the acceptor atoms or molecules. The exchange interaction
between the donor D and acceptor A involves a transition state with a D–A
distance that is close to the sum of the gas-kinetic collision radii of D and A,
respectively.
5. Photochemistry refers to the study of those specific chemical reactions
which result after the distinctive exposure of light radiations.
6. In photochemical reactions, the visible and UV radiations of 2000-
8000Å wavelength are generally used.
7. Photosensitization is referred as the process of initiating a reaction through
the use of a substance capable of absorbing light and transferring the
energy to the desired reactants.
8. A photosensitizer is a molecule that produces a chemical change in
another molecule in a photochemical process.
9. Actinometers are the devices specifically used for measuring the heating
power of radiation and also used in meteorology for measuring the solar
radiation as pyranometers, pyrheliometers and net radiometers.
10. Chemical actinometry includes measuring radiant flux via the yield from a
chemical reaction. It essentially requires a chemical with a known quantum
yield and easily analyzed reaction products.
11. The actinometers are mostly used in meteorology for measuring solar
radiation that is transmitted by the sun, reflected by the earth or scattered
by the atmosphere, in photochemical experiments that involve complex
irradiation geometry, and for calibrating photochemical detectors used for
radiation measurements.
5.7 SUMMARY
 Energy transfer refers to a process in which an excited atom or molecule

(donor) transfers its excitation energy to an acceptor atom or molecule
during the lifetime of the donor excited state.
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112 Material
 If the acceptor is a luminescent species, it can emit by virtue of energy Energy Transfer
Mechanisms
transfer, i.e., the acceptor luminesces as a result of the excitation of the
donor. Such a luminescence is called ‘sensitized luminescence’, and some
places it is also used as ‘sensitizer’ and ‘activator’ instead of ‘donor’ and
‘acceptor’. NOTES
 Energy transfer processes occur via radiative or non-radiative
mechanisms.This mechanism involves the absorption of light by a donor
atom or molecule (D) followed by emission of a photon by the donor and
the absorption of the emitted photon by another molecule called the acceptor
(A).
 The radiative mechanism is important if the acceptor A absorbs at the
wavelength at which the donor emits. The efficiency of the process is
determined simply by the quantum yield of the donor luminescence and the
absorbance of the acceptor at the donor emission wavelength.
 The radiative mechanism is a trivial case of energy transfer because it can
be characterized by measuring the donor absorption and the acceptor
emission separately from each other.
 The Dexter Exchange Mechanism involves a direct contact between the
donor and the acceptor atoms or molecules. The exchange interaction
between the donor D and acceptor A involves a transition state with a D–A
distance that is close to the sum of the gas-kinetic collision radii of D and A,
respectively.
 The energy transfer efficiency is strongly dependent on the spectral overlap
between the donor emission and the acceptor absorption.
 Photochemistry refers to the study of those specific chemical reactions which
result after the distinctive exposure of light radiations. Principally, the light
provides the essential energy that is required by the photochemical reactions
to take place.
 In photochemical reactions, the visible and UV radiations of 2000-8000Å
wavelength are generally used.
 In chemistry, typically in several photochemical reactions the usually the
reacting matter or substance does not directly absorb radiation, however it
obtains the essential energy from some of the other different external
substance or matter which have light absorbing properties.
 These external substance or matter is acknowledged as sensitizer. Therefore,
when the photosensitized is absent then no reaction can occur because it is
not possible for the reacting substance or matter to absorb its own radiation.
 Due to this the solutions of exothermic reactions become hotter. In a
chemiluminescent reaction, the direct product of the reaction is an excited
electronic state.
Self-Instructional
Material 113
Energy Transfer  Chemiluminescence differs from fluorescence or phosphorescence in respect
Mechanisms
that the electronic excited state is the product of a chemical reaction rather
than of the absorption of a photon.
 Actinometers are the devices specifically used for measuring the heating
NOTES
power of radiation and also used in meteorology for measuring the solar
radiation as pyranometers, pyrheliometers and net radiometers.
 The name actinometer is commonly given to devices that are used in the
ultraviolet and visible wavelength ranges. For example, solutions of iron or
Fe (III) oxalate can be used as a chemical actinometer, while bolometers,
thermopiles, and photodiodes are physical devices which provide a reading
that can be correlated to the number of photons detected.
 In chemistry, an actinometer is defined as a device that is used to measure
the intensity of solar radiation. It is a chemical system that determines the
number of photons by measuring the rate of change of photoinduced
responses in a chemical system.
 Light in the wavelength range of about 2,080 to 4,350 angstroms, i.e.,
ultraviolet to violet light decomposes the oxalic acid into a mixture of carbon
dioxide, carbon monoxide and water through a complex process involving
initial absorption of the light energy by the uranyl ion.
 Generally, a standard solution is irradiated with light of the proper wavelength
and of known intensity, and then the quantity of oxalic acid decomposed is
accurately measured by titration with potassium permanganate.
5.8 KEY WORDS
 Radiative mechanisms: Radiative mechanism involves the absorption of

light by a donor atom or molecule (D) followed by emission of a photon by
the donor and the absorption of the emitted photon by another molecule
called the acceptor (A).
 Photochemistry: Photochemistry refers to the study of those specific
chemical reactions which result after the distinctive exposure of light
radiations.
 Photosensitization: Photosensitization is referred as the process of initiating
a reaction through the use of a substance capable of absorbing light and
transferring the energy to the desired reactants.
 Photosensitizer: A photosensitizer is a molecule that produces a chemical
change in another molecule in a photochemical process.
 Chemiluminescence: Chemiluminescence, also termed as
chemoluminescence, is the emission of light (luminescence) which occurs as
the result of a chemical reaction.
Self-Instructional
114 Material
 Actinometers: Actinometers are the devices specifically used for measuring Energy Transfer
Mechanisms
the heating power of radiation and also used in meteorology for measuring
the solar radiation as pyranometers, pyrheliometers and net radiometers
NOTES
EXERCISES

1. What is energy transfer?
2. With the help of a diagram show the energy transfer from a donor (D) to
an acceptor (A).
3. What is photochemistry?
4. Write short notes on the following:
i. Photosensitization
ii. Chemiluminescence
5. Give some points that shows the significance of photosensitizer.
6. What is chemical actinometry.
1. Explain the energy transfer mechanism in detail.
2. Distinguish between radiative mechanisms and non-radiative mechanisms.
3. Write a detailed note on photosensitization and chemiluminescence
4. Explain the mechanism of photosensitization reactions.
5. Discuss about the liquid phase reactions.
6. Give a detailed note on actinometers .
7. Explain the working principle of chemical actinometer

& Company Ltd. Self-Instructional
Material 115
Flash Photolysis
UNIT 6 FLASH PHOTOLYSIS

NOTES Structure
6.0 Introduction
6.1 Objectives
6.2 Flash Photolysis
6.3 Study of Photochemical Reactions in Different Areas
6.4 Hydrogen-Halogen Reaction, Decomposition of Carbonyl Compounds
6.6 Summary
6.7 Key Words
6.0 INTRODUCTION
Flash photolysis is a pump-probe laboratory technique, in which a sample is firstly
excited by a strong pulse of light from a laser of nanosecond, picosecond,
or femtosecond pulse width or by a short-pulse light source such as a flash lamp.
Flash photolysis was developed shortly after World War II as a result of the
military’s attempts to build cameras fast enough to photograph missiles in flight.
Flash photolysis is often used to study reactions that are light dependent
such as photosynthesis and reactions in the cones on the retina of our eye, but the
method can also be applied to other reactions. Flash photolysis is frequently used
to analyse reactions that are light dependent, such as photosynthesis and reactions
that occur in the cones on the retina of our eye. The laser pulse must be
approximately half the length of the reaction, and of sufficient energy to induce the
reaction to take place.
In this unit, you will study about flash photolysis, study of photochemical
reactions, hydrogen- halogen reaction, decomposition of carbonyl compounds in
detail.
6.1 OBJECTIVES
 Understand what flash photolysis is
 Evaluate the significance of photochemical reactions
 Explain hydrogen-halogen reaction and decomposition of carbonyl
compounds
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Flash Photolysis
6.2 FLASH PHOTOLYSIS
Flash photolysis is a pump-probe laboratory technique, in which a sample is firstly
excited by a strong pulse, termed as pump pulse, of light from NOTES
a laser of nanosecond, picosecond, or femtosecond pulse width or by a short-
pulse light source, such as a flash lamp. The first strong pulse that is produced by
a short-pulse light source starts a chemical reaction which leads to an increased
population for energy levels other than the ground state within a sample of atoms
or molecules. Typically the absorption of light by the sample is recorded within
short time intervals, termed as test pulses, to monitor relaxation or reaction processes
initiated by the pump pulse.
Flash photolysis was developed shortly after World War II as a result of
the military’s attempts to build cameras fast enough to photograph missiles in flight.
The technique was developed in 1949 by Manfred Eigen, Ronald George
Wreyford Norrish and George Porter, who won the 1967 Nobel Prize in
Chemistry for this invention. Over the next 40 years the technique became more
powerful and sophisticated due to developments in optics and lasers. Also, the
interest in this method grew considerably as the practical applications expanded
from chemistry to areas, such as biology, materials science, and environmental
sciences. Today flash photolysis facilities are extensively used by researchers to
study light-induced processes in organic molecules, polymers, nanoparticles,
semiconductors, photosynthesis in plants, signaling, and light-induced
conformational changes in biological systems.
Flash photolysis is also frequently used to analyse reactions that are light
dependent, such as photosynthesis and reactions that occur in the cones on the
retina of our eye, but this method can also be applied to other reactions. The light
in the form of a laser excites a molecule into a reactive state, usually in the form of
a free radical. From there it is possible to measure the reaction spectroscopically,
using the exitory flash as a light source to measure absorbance. The laser pulse
must be approximately half the length of the reaction, and of sufficient energy to
induce the reaction to take place. Further the flash must cover the spectrum of
frequencies which are being studied because not only is the flash producing
intermediates of the reaction that are usually not observed, it is also producing the
source for spectroscopic analysis. Intermediates of most reactions are rarely
observed, this techniques isolates even low concentrations of otherwise
unobservable portions of reactions allowing research into synthetic, biochemical,
and photo-sensitive reactions.
Flash Photolysis using the LP980 Spectrometer
In flash photolysis, a short pulse of light generates a transient (temporary) species
in a sample, for example, a radical intermediate or a short-lived excited state. As
the sample relaxes back to the ground state or the final reaction products, the
changes occurring are recorded as a function of time using a spectroscopic
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Flash Photolysis technique. A flash photolysis spectrometer typically monitors the change in
absorption as a function of time, utilising a second light source (probe) besides the
excitation (pump) pulse going through the sample ith references to real life
applications.
NOTES This technique is also known as Transient Absorption (TA). Transient
absorption can be performed in a wide range of timescales, from picoseconds to
seconds. Experiments in the nanosecond to seconds range have many applications
involving detection of free radicals, excited states, and charge transfer reaction
intermediates. It is the technique of choice to study reaction kinetics, the lifetimes
of non-emissive triplet states, and to detect elusive intermediates in light-triggered
processes.
Therefore it is very useful in fundamental photochemistry, materials science, and
photobiology. For these type of studies, the specific laser flash photolysis instruments
are used. As shown below, the Edinburgh Instruments LP980 is an example of
compatible laser flash photolysis instrument which provides an accurate
approximation.
The LP980 Spectrometer
The basic components of a flash photolysis system are light sources that act as an
optical pump and probe, a monochromator and a detector. The LP980 integrates
all of these components into one instrument, as shown in Figure 6.1.
Fig. 6.1 Edinburgh Instruments LP980 Spectrometer

In LP980, the pump pulse creates the transient excited species and acts as time
zero for the experiment. Typically a laser of high energy and nanosecond pulses is
used, such as Nd:YAG. The LP980 provides flexibility that are compatible for
different lasers. The steering chamber of LP980 helps in easily aligning the pump
laser into the sample chamber and to change and adjust between the different
optical configurations. The probe beam is produced by a white-light source in
order to analyse the absorption at different wavelengths. The LP980 features a
xenon lamp that can be used in continuous or pulsed mode for higher energy and
is compatible transient absorption helps in analysing liquids, solids or gas cells by
changing the sample holder and optical configuration. Different sample configuration
options for the LP980 are shown in Figure 6.2.
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Flash Photolysis
NOTES
Fig. 6.2 Optical Configurations for Transient Absorption in the LP980 Spectrometer
In the above Figure 6.2 is illustrated the optical configurations for transient
absorption in the LP980 spectrometer, and the pump and probe beam geometries
at the sample position.
The LP980 provides the unique option of a Photo Multiplier Tube (PMT) and
Intensified CCD Camera (ICCD) simultaneously mounted on the same
monochromator, so that the analyst can easily alternate between spectral (ICCD)
and time-resolved (PMT) acquisition. The different types of PMT detector, camera
and oscilloscope models are available. Data averaging, which is essential in TA,
can be carried out either by the oscilloscope or the computer.
Laser flash photolysis is a versatile technique for the study of time-resolved
processes in the range of nanoseconds to seconds. It complements time-resolved
luminescence as in some cases absorption is a better choice of detection method.
The large time range covered by a flash photolysis spectrometer results in a huge
variety of potential applications, from reaction kinetics to photophysics studies.
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Flash Photolysis
Check Your Progress

1. What is flash photolysis?
NOTES 2. Where is flash photolysis used nowadays?
3. How is flash photolysis conducted?
4. Give the function of spectrometer.
6.3 STUDY OF PHOTOCHEMICAL REACTIONS IN

DIFFERENT AREAS
Characteristically, the photochemical reaction is defined as a chemical reaction

which is initiated or originated through the absorption of energy that is in the form
of light. The consequence or significance of molecules’ that absorb the light is
defined as the formation of transient excited states (molecules) who have different
chemical and physical properties as compared to the original molecules. Thus, the
formation of new chemical species may have different state of form, can modify
into new structures or can combine or associate either with each other or with
other molecules, and can transfer electrons, hydrogen atoms, protons and even
the electronic excited energy to other molecules. Excited states of the molecules
are considered as stronger acids and stronger reductants as compared to the
Primarily, the chemical nature of a molecule is defined on the basis of its

electrons. If the total energy of a molecule’s electrons, i.e., its electronic energy
can accept only certain distinctive values, then the energy is said to be quantized.
Photochemistry is the branch of chemistry that is concerned with the chemical
effects of light. Generally, this term is used to describe a chemical reaction that is
caused by absorption of ultraviolet (wavelength from 100 to 400 nm), visible light
(400–750 nm) or infrared radiation (750–2500 nm). Photochemical reactions
advance differently than temperature driven reactions.
Photoexcitation is considered as the first step in a photochemical process

where the reactant is elevated to a state of higher energy, termed as an excited
state. The first law of photochemistry states that light must be absorbed by a
chemical substance in order for a photochemical reaction to take place. According
to the second law of photochemistry, for each photon of light absorbed by a
chemical system, not more than one molecule is activated for a photochemical
reaction.
Photochemical Reactions
Photochemical reactions are very important in many areas chemistry. Examples in
atmospheric environmental chemistry include the production of ozone in the
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stratosphere, the decomposition of chlorofluorocarbons in the stratosphere, and Flash Photolysis
the oxidation of sulfur species with photochemically generated hydroxyl radicals

in the troposphere. An example in aqueous environmental chemistry is the speciation
of Fe(II) and Fe(III).
Photochemistry is very useful in synthetic chemistry. Often photochemically NOTES
driven reactions provide different products than thermally driven reactions. An
example from synthetic chemistry is the use of photochemically generated
methylene singlet and triplet intermediates. Absorption of light by molecules
produces electronic excited states. Electronically excited molecules can be very
reactive. As a consequence, photochemical reactions are often very rapid. Fast
reaction techniques are required to study these processes.
Flash photolysis is a commonly used fast reaction technique for
photochemical reactions. For reactions with a moderate rate, flash lamps provide
sufficient time response. An example of a typical flash lamp is the xenon lamp in a
standard camera. For very fast reactions, however, the slow decay time of the
light emission from a flash lamp covers the progress of the reaction. In general the
pulse width of the light source must be much shorter than the half-time of the
chemical reaction. The pulse width of xenon flash lamps, such as those used in
photography, is in the microsecond time scale. For faster reactions, specially
designed lasers must be used that have pulse widths in the nanosecond range.
Using ultra-fast pulsed lasers allows processes in the sub-femtosecond time
scale to be studied. In some of the laser flash-photolysis system the lasers have
pulse widths in the 10 nanosecond range, which allows a wide range of
photochemical processes to be studied.
One disadvantage of laser driven systems is that ultraviolet lasers have a
fixed wavelength. Reactants in photochemical reactions can have a wide variety
of absorption wavelengths, some of which may not be accessible to a given laser
source. Therefore, several different types of lasers are often necessary to provide
coverage of the UV range of common organic and inorganic reactants.
Photoreduction of Benzophenone
The electronic energy level diagram for a typical molecule is shown in Figure 6.3.
The closely spaced horizontal lines represent the different vibrational states of the
given electronic state.
Fig. 6.3 Typical Electronic Energy Level Diagram

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Flash Photolysis Benzophenone undergoes rapid intersystem crossing to the triplet state, which has
a long half-life. Fluorescence is not observered for benzophenone.
Phosphorescence is observed at liquid nitrogen temperature, while only very weak
phosphorescence is observed at room temperature (in water and isooctane). At
NOTES room temperature, photochemical reactions and nonradiative processes are
responsible for the quenching of the phosphorescence.
(1)
The reaction is done in 50:50 isopropanol-water as a solvent. The α-hydrogen of
isopropanol is transferred to the very reactive excited state to produce the
protonated benzophenone ketyl , which is a free radical.
Dimerization of the free radicals gives the reaction product, benzpinacol.
(2)
(3)
The k1 rate constant is measured in acidic solution. The other product of the initial
proton transfer from isopropanol, , is a protonated acetone ketyl.
This free radical may disproportionate to form acetone and isopropyl alcohol, or
the free radical may also react with benzophenone to produce another molecule of
the protonated benzophenone ketyl (C6H5)2CO•H. Reaction (3) is monitored by
following the disappearance of the absorption of the protonated ketyl (C6H5)2CO•H
at 545 nm. However, the protonated benzophenone ketyl (C6H5)2CO•H is a weak
acid. In basic solution, the protonated ketyl is deprotonated:
(4)
At pH values greater than 8 the production of product is through the following
reaction rather than Reaction (3):
(5)
The deprotonated benzophenone ketyl, , has an absorbance
maximum at 630 nm. Kinetics studies in basic solution use 630 nm to follow the
time course of the reaction.
Kinetics Analysis
Reaction (3) is considered as a second order reaction. The rate law is given by,
(6)
Here AH is the protonated benzophenone ketyl. On integration the Reaction (6)

gives:
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Flash Photolysis
(7)
According to Reaction (7), for a second order reaction, a graph of 1/[A] verses t NOTES
must yield a straight line. This is an appropriate form if the experiment is conducted
in acidic solution at 545 nm. In basic solution, Reaction (5) is considered of first
order in and , thus providing,
(8)
Here A is considered as the deprotonated form. The concentration of the

deprotonated form is analysed or evaluated from the acid dissociation constant
for the equilibrium given in Reaction (4):
(9)
(10)
The Ka for the protonated benzophenone ketyl is 6 1010. When the acid-base
reaction is faster as compared to the photochemical reaction, then Reaction (10)
can be substituted into Reaction (8) to obtain,
(11)
Defining kobs as,
(12)
Thus, it provides the second order rate law as follows,
In the basic solution at 630 nm, the kobs can be evaluated by a graph of 1/[A]
verses t. Self-Instructional
Material 123
Flash Photolysis
Check Your Progress

5. State the law of photochemical equivalence.
NOTES 6. Where is law of photochemical equivalence applicable?
7. Where is Einstein law usually marked ?
6.4 HYDROGEN-HALOGEN REACTION,

DECOMPOSITION OF CARBONYL
COMPOUNDS
A few photochemical reactions will be briefly discussed in this section.

1. Photolysis of Ammonia: The decomposition of ammonia takes place by
radiations of wave length from 1600–2000 Å. The average quantum yield
up to 500 mm pressure of ammonia is 0.25. Wing has suggested the following
mechanism:
NH3. + hv  NH2 + H (primary process) (13)
NH2. +  NH3 (14)
H. + H.  H2 (15)
NH2. + NH2.  N2H4 (16)
N2H4. + H  NH3 + NH2 (17)
NH2 + NH2  N2 + 2H2 (18)
The low observed quantum yield may be due to the fact that the products
of the primary stage NH2 and H recombine to form ammonia.
2. Decomposition of Hydrogen Iodide in the Gaseous Phase: From the
studies of molecular spectra, it is clear that one molecule of HI absorbs
light of wave length less than 4000 Å, the molecule dissociates into an atom
of hydrogen and an atom of iodine, the latter is in the excited state. The
reaction has been extensively studied by E Warburg.
The primary process of the reaction is therefore
hv
HI   H. + I.
The possible secondary processes that follow this step are:
HI + H+  H2 + I. (19)
I + HI  I2 + H (20)
H + H.  H2 (21)
I. + I.  I2 (22)
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I. + H.  HI (23)
124 Material
In the above reactions, (21) and (23) are highly exothermic with the result Flash Photolysis
that the dissociate unless the reaction has taken place in the presence of
third atom. Such three body collisions are however, unlikely. Reaction (20)
is an endothermic process and therefore takes place slowly. The elimination
of these three reactions leave reactions (19) and (22) as the likely secondary NOTES
processes. The decomposition of HI can now be written as consisting of a
primary and two secondary processes:
hv
HI   H.+ I *
HI + H  H2 + I
I + I  I2
On adding these three equations, we get:
hv
2HI   H2 + I2
Thus, the absorption of one quantum of radiation leads to the decomposition
of two hydrogen iodide molecules. This agrees with the measured quantum
efficiency.
3. The Hydrogen-Chlorine Reaction: If a mixture of hydrogen and chlorine
is exposed to visible or ultra-violet light of wave length less than 4800 Å, a
fast reaction occurs resulting in the formation of hydrogen chloride.
The first step involves the dissociation of chlorine molecule and is followed
by other fast steps:
Cl2 + hv  2Cl (24)
Cl + H2  HCl + H (25)
H + Cl2  HCl + Cl (26)
1
Cl (at walls)  Cl2 (27)
2
The quantum yield of the reaction is exceptionally high (104 to 106). Once
the reaction has been started by the absorption of one quanta, of light, a
very large number of hydrogen chloride molecules are formed as a result of
the continued repetition of steps (25) and (26) of reactions. The chain is
only terminated at the walls of the reaction vessel.
4. Dimerization of Anthracene in Solution: When anthracene in benzene
solution is exposed to UV light; dimerization occurs and dianthracene is
formed.
2C14H10 + hv  C28H20
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Flash Photolysis
NOTES
Fig. 6.5 Dimerization of anthracenes
In dilute solution, the reaction is accompanied by fluorescence and the

quantum efficiency is small, but as the concentration is increased, the
fluorescence falls off where as the efficiency increases towards a limiting
value. When the latter is attained, there is very little fluorescence. The results
can be shown quantitatively by the curves in Figure 6.5.
5. Double Decomposition: Hexahydrobenzene, in the presence of bromine,
illuminated by light of wave length 4760 Å, gives monobromo-
hexahydrobenzene and hydrogen bromide and hydrogen bromide.
hv
C6H12 + Br2   C6H11Br + HBr
The photochemical hydrolysis of monochloroacetic acid is another example
of such a reaction,
hv
CH2Cl.COOH + H2O   CH2(OH)COOH + HCl
6. Isomeric Transformation: Some substances, when photolysed, are
transformed to the isomeric form, such as conversion of maleic acid into
fumaric acid and the reverse reaction, by exposing their aqueous solutions
to light of wave length 2070 Å, 2530 Å and 2820 Å.
7. Chain Reactions: A chain reaction often but not always leads to a

complicated rate law. Let us consider a reaction between hydrogen and
bromine
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The overall reaction is Flash Photolysis
H2 + Br2 = 2HBr
The rete law for this reaction is given by the equation
d[HBr] k[ H2 ][ Br2 ]1 / 2 NOTES
=
dt I  k |HBr |[ Br2 ]
This expression is complicated which certainly suggests that a chain
mechanism is involved. The mechanism that has been proposed is as follows.
ka
Initiation (a) Br2   2Br..
kb
Propagation (b) Br + H2  HBr + Ha
kc
(c) Ha + Br2  HBr + Bra
kd
Inhibition (d) Ha + HBr   H2 + Bra
ke
Termination (c) Bra + Br.  Br2
In order to obtain the rate law from this mechanism we have to find the rate
of formation of HBr. Since it is generated in reactions (b) and (c) but removed in
reaction (d). The net rate of formation is
d [HBr]/dt = Kb[Br][H2] + kc [H][Br2] – kd [H] [HBr]
In order to develop this expression we must find the concentrations of
bromine and hydrogen atoms. This can be done by first setting up the two rate
equations for the concentrations of [H] and [Br] and then by imposing the steady
state approximation
d[H]/dt = kb [H2] [Br] – kc [H] [Br2] – kd [H] [HBr] = 0
d[Br]/dt = 2ka [Br2] – kb [Br] [H2]+ kc [H] [Br2] + kd [H] [HBr] – 2Kc
[Br]2 = 0
on solving these two simultaneous equations for [H] and [Br]. These values
are substituted in d[HBr]/dt. The result is
1/ 2
d[HBr] 2kb ka / ka [H2 ][Br2 ]1 / 2
=
dt 1  K d [HBr]/ kc [Br2 ]
This has the same form as the empirical rate law and the two observed rate
coefficients can be expressed as
k = 2kb(ka/kc)1/2
k = kd/kc
Some chain reactions have simple kinetics yet lot of care has been taken in
analysing the data of chemical kinetics.
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Flash Photolysis For example the dehydrogenation of ethane proceeds as under
C2H6  C2H4 + H2
Experimentally the reaction has been found to be first order, i.e.,
NOTES d C2 H6
= k [C2H4]
dt
During the course of reaction the free radicals have been detected the
following mechanism has been proposed to account for the observed results.
ka
Initiation C2H6   2CH3
k
PropagationCH3 + CH3 – CH3 b
 CH4 + CH3CH2
kc
CH3CH2  CH2CH2 + H
kd
H + CH3CH3   H2 + CH3CH2
ke
Termination H + CH3CH2  CH3CH3
The reaction mechanism can be analysed by setting up the appropriate rate
equations and applying the steady approximation for all the radical species. The
rate equation is
d[CH3CH3 ]
= (ka kc kd/2kc)1/2 [CH3CH3]
dt
This is in accord with the first kinetics.
Hg + hv  Hg*
Hg* + H2  Hg + 2H
where Hg* represents an activated mercury atom. The most important
example of photosensitization is the action of chlorophyll in the combination of
carbon dioxide and water in presence of sun light. The process is known as photo
synthesis.
Check Your Progress

8. What is photolysis of ammonia ?
9. Write about decomposition of hydrogen iodide.
10. What is hydrogen-chlorine reaction?

QUESTIONS
1. Flash photolysis is a pump-probe laboratory technique, in which a sample
is firstly excited by a strong pulse (called pump pulse) of light from
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a laser of nanosecond, picosecond, or femtosecond pulse width or by a Flash Photolysis
short-pulse light source such as a flash lamp.

2. Today flash photolysis facilities are extensively used by researchers to study
light-induced processes in organic molecules, polymers, nanoparticles,
semiconductors, photosynthesis in plants, signaling, and light-induced NOTES
conformational changes in biological systems.
3. In flash photolysis, a short pulse of light generates a transient (temporary)
species in a sample, for example, a radical intermediate or a short-lived
excited state.
4. A flash photolysis spectrometer typically monitors the change in absorption
as a function of time, utilising a second light source (probe) besides the
excitation (pump) pulse going through the sample ith references to real-life
applications.
5. The law of photochemical equivalence or the principle of quantum activation
states: Each quantum of radiation absorbed by a molecule activates one
molecule in the primary step of photochemical process.
E = Nhv
6. The law of photochemical equivalence is applicable only to primary
photochemical process, i.e., when as a result of absorption of light, only
one molecule decomposes and the products enter no further reaction.
7. The Einstein law is usually marked by secondary reactions and radiative
and non-radiative transitions which present a simple 1 : 1 relationship between
the number of photon absorbed and the number of molecules of final products
in the reaction.
8. Photolysis of ammonia is the decomposition of ammonia takes place by
radiations of wave length from 1600–2000 Å. The average quantum yield
up to 500 mm pressure of ammonia is 0.25.
9. Decomposition of hydrogen iodide in the gaseous phase is the studies of
molecular spectra, it is clear that one molecule of HI absorbs light of wave
length less than 4000 Å, the molecule dissociates into an atom of hydrogen
and an atom of iodine, the latter is in the excited state.
10. The hydrogen-chlorine reaction is a mixture of hydrogen and chlorine is
exposed to visible or ultra-violet light of wave length less than 4800 Å, a
fast reaction occurs resulting in the formation of hydrogen chloride.
6.6 SUMMARY
 Flash photolysis is a pump-probe laboratory technique, in which a sample

is firstly excited by a strong pulse, termed as pump pulse, of light from
a laser of nanosecond, picosecond, or femtosecond pulse width or by a
short-pulse light source, such as a flash lamp.
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Material 129
Flash Photolysis  The first strong pulse that is produced by a short-pulse light source starts
a chemical reaction which leads to an increased population for energy levels
other than the ground state within a sample of atoms or molecules.
 Typically the absorption of light by the sample is recorded within short time
NOTES
intervals, termed as test pulses, to monitor relaxation or reaction processes
initiated by the pump pulse.
 Flash photolysis was developed shortly after World War II as a result of
the military’s attempts to build cameras fast enough to photograph missiles
in flight.
 Intermediates of most reactions are rarely observed, this techniques isolates
even low concentrations of otherwise unobservable portions of reactions
allowing research into synthetic, biochemical, and photo-sensitive reactions.
 In flash photolysis, a short pulse of light generates a transient (temporary)
species in a sample, for example, a radical intermediate or a short-lived
excited state. As the sample relaxes back to the ground state or the final
reaction products, the changes occurring are recorded as a function of time
using a spectroscopic technique.
 A flash photolysis spectrometer typically monitors the change in absorption
as a function of time, utilising a second light source (probe) besides the
excitation (pump) pulse going through the sample ithreferences to real life
applications.
 The steering chamber of LP980 helps in easily aligning the pump laser into
the sample chamber and to change and adjust between the different optical
configurations. The probe beam is produced by a white-light source in order
to analyse the absorption at different wavelengths.
 The LP980 features a xenon lamp that can be used in continuous or pulsed
mode for higher energy and is compatible transient absorption helps in
analysing liquids, solids or gas cells by changing the sample holder and
optical configuration.
 Photochemistry is very useful in synthetic chemistry. Often photochemically
driven reactions provide different products than thermally driven reactions.
An example from synthetic chemistry is the use of photochemically generated
methylene singlet and triplet intermediates.
 Absorption of light by molecules produces electronic excited states.
Electronically excited molecules can be very reactive. As a consequence,
photochemical reactions are often very rapid. Fast reaction techniques are
required to study these processes.
 Flash photolysis is a commonly used fast reaction technique for
photochemical reactions. For reactions with a moderate rate, flash lamps
provide sufficient time response. An example of a typical flash lamp is the
xenon lamp in a standard camera.
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 Benzophenone undergoes rapid intersystem crossing to the triplet state, Flash Photolysis
which has a long half-life. Fluorescence is not observered for benzophenone.

Phosphorescence is observed at liquid nitrogen temperature, while only
very weak phosphorescence is observed at room temperature (in water
and isooctane). NOTES
6.7 KEY WORDS
 Photolysis of ammonia: Photolysis of ammonia is the decomposition of

ammonia takes place by radiations of wave length from 1600–2000 Å.
The average quantum yield up to 500 mm pressure of ammonia is 0.25.
 Decomposition of hydrogen iodide: Decomposition of hydrogen iodide
in the gaseous phase is the studies of molecular spectra, it is clear that one
molecule of HI absorbs light of wave length less than 4000 Å, the molecule
dissociates into an atom of hydrogen and an atom of iodine, the latter is in
the excited state.
 Hydrogen-chlorine reaction: The hydrogen-chlorine reaction is a mixture
of hydrogen and chlorine is exposed to visible or ultra-violet light of wave
length less than 4800 Å, a fast reaction occurs resulting in the formation of
hydrogen chloride.
 Photochemical equivalence law: The law of photochemical equivalence
or the principle of quantum activation states: Each quantum of radiation
absorbed by a molecule activates one molecule in the primary step of
photochemical process.
E = Nhv
 Flash photolysis: Flash photolysis is a pump-probe laboratory technique,
in which a sample is firstly excited by a strong pulse of light from
a laser of nanosecond, picosecond, or femtosecond pulse width or by a
short-pulse light source such as a flash lamp.

EXERCISES

1. What is flash photolysis?
2. Brief a note on laser photolysis.
3. Give short note on LP980 Spectrometer.
4. What are the areas where flash photolysis used?
5. What is photolysis of ammonia?
6. Brief a note on double decomposition.
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Material 131
Flash Photolysis Long Answer Questions
1. Elaborate a note on flash photolysis.
2. Explain with the help of diagram the optical configurations for transient
NOTES absorption in the LP980 spectrometer.
3. Discuss flash photolysis using the LP980 spectrometer.
4. List the different areas where photochemical reactions are used.
5. Explain Photoreduction of Benzophenone.
6. Write a detailed note on photochemical reactions. Also give the relevant
equations and diagrams related to it.
7. Discuss in detail about hydrogen-halogen reaction and decomposition of
carbonyl compounds

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Radiation Chemistry
UNIT 7 RADIATION CHEMISTRY

Structure NOTES
7.0 Introduction
7.1 Objectives
7.2 Radiation Chemistry of Aqueous Solutions-Hydrated Electron
7.3 Radiolysis of Water
7.4 Pulsed Radiolysis
7.6 Summary
7.7 Key Words
7.0 INTRODUCTION
Radiation chemistry involves the study of nuclear reactions. There are clear
differences between a chemical reaction, and a nuclear reaction, a chemical reaction
involves electrons of an atom, while a nuclear reaction involves a reaction within
the nucleus of an atom. Marie Curie discovered radioactivity, which is the
spontaneous disintegration of the unstable nuclei of some elements, or isotopes of
elements, into more stable nuclei. As ionizing radiation moves through matter its
energy is deposited through interactions with the electrons of the absorber. The
result of an interaction between the radiation and the absorbing species is removal
of an electron from an atom or molecular bond to form radicals and excited species.
Both the harmful effects of radiation upon biological systems and the useful
effects of radiotherapy involve the radiation chemistry of water. The vast majority
of biological molecules are present in an aqueous medium; when water is exposed
to radiation, the water absorbs energy, and as a result forms chemically reactive
species that can interact with dissolved substances (solutes). Water is ionized to
form a solvated electron and H2O+, the H2O+ cation can react with water to form
a hydrated proton (H3O+) and a hydroxyl radical (HO.).
In this unit, you will study about radiation chemistry of aqueous solutions-
hydrated electron, radiolysis of water, pulsed radiolysis in detail.
7.1 OBJECTIVES
 Explain radiation chemistry of aqueous solutions-hydrated electron
 Understand radiolysis of water
 Discuss pulsed radiolysis
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Radiation Chemistry
7.2 RADIATION CHEMISTRY OF AQUEOUS
SOLUTIONS-HYDRATED ELECTRON
NOTES Radiation chemistry involves the study of nuclear reactions. There are clear
differences between a chemical reaction, and a nuclear reaction, a chemical reaction
involves electrons of an atom (which orbit the nucleus), while a nuclear reaction
involves a reaction within the nucleus of an atom (which consists of protons and
neutrons). Marie Curie discovered radioactivity, which is the spontaneous
disintegration of the unstable nuclei of some elements, or isotopes of elements,
into more stable nuclei.
Isotopes are different forms of an element which contain the same number of
protons as the element on the periodic table, but each isotope of the element
contains a different number of neutrons (thus isotopes have varying mass numbers).
Generally, all isotopes with an atomic number over 83 are considered radioactive.
Because a great amount of energy holds the nucleus together, in a nuclear reaction,
a great amount of energy is released as the nucleus is disintegrated: this energy is
called the binding energy. The term radiation refers to the particles and energy
that are released as a result of the radioactive reaction.
It is important to note that in a radioactive reaction, as in almost all reactions,

the law of conservation of mass applies, which means that the total mass before
the reaction has to equal the total mass after the reaction occurs. This concept is
key in understanding radioactive reactions.
To understand the notation of nuclear reactions, it is helpful to review what
mass number, and atomic number refer to, and how they are represented along
with the chemical symbol of an atom. Mass number refers to the total number of
neutrons and protons in a nucleus, and atomic number refers to the total number
of protons in the nucleus. Given a nucleus X, mass number and atomic number will
be denoted as follows:
Also, an isotope of element X with mass number of 50, for example, may be
written as X-50.
There are three primary types of nuclear reactions:
 Alpha Decay
 Beta Decay
 Gamma Radiation
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These three main types of radiation are outlined below: Radiation Chemistry
Alpha Decay
In alpha decay, an unstable radioactive nucleus releases an alpha particle, which is
essentially a helium nucleus, and therefore the alpha particle has a mass number of NOTES
4 and an atomic number of 2, and can be denoted in either one of the two ways
shown below:
Because of the law of conservation of mass, the new nucleus has a mass
number that is four less than that of the initial nucleus, and an atomic number that is
decreased by two. In layman’s terms, if you add the mass numbers on one side of
the equation, they should equal the mass number on the other side of the equation,
and the same goes for atomic numbers.
In an alpha radiation problem, often you are given only the initial unstable
nucleus and asked to figure out the resulting nucleus. You know an alpha particle is
released, so you use the law of conservation of mass to figure out the missing
nucleus. Once you have found the missing nucleus, you can then use its atomic
number to identify the element
Mass number of unknown nucleus: 227 – 4= 223

Atomic number of unknown nucleus: 88 – 2= 86
If we look on the periodic table, Radon (Rn) has an atomic number of 86
Therefore, our complete reaction is:
Beta Decay
In beta decay, an unstable radioactive nucleus releases a beta particle, which is an
electron. An electron has no mass, thus it has no mass number, and essentially a -
1 atomic number, due to the -1 charge of an electron:
In much the same way as we solved the alpha decay reaction, we can solve for the
new nucleus in beta decay
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Radiation Chemistry Gamma Decay
In gamma decay, a high-energy photon is released. Radioisotopes, used in medicine
for uptake in a person’s body to detect key organs and glands, are frequently
NOTES made by gamma reactions. A gamma particle is:

Thus, in this type of radiation, there is no change in mass number or atomic number-
the nucleus stays the same, and there is just a release of energy. Here is an example
of a gamma reaction, again following the law of conservation of mass:
Other nuclear particles (besides the alpha, beta and gamma particles) seen in
nuclear reactions include:
Radiation Interactions with Matter

As ionizing radiation moves through matter its energy is deposited through
interactions with the electrons of the absorber. The result of an interaction between
the radiation and the absorbing species is removal of an electron from an atom or
molecular bond to form radicals and excited species. The radical species then
proceed to react with each other or with other molecules in their vicinity. It is the
reactions of the radical species that are responsible for the changes observed
following irradiation of a chemical system.
Charged radiation species Interact through Coulombic forces between the
charges of the electrons in the absorbing medium and the charged radiation particle.
These interactions occur continuously along the path of the incident particle until
the kinetic energy of the particle is sufficiently depleted. Uncharged species (
photons, x-rays) undergo a single event per photon, totally consuming the energy
of the photon and leading to the ejection of an electron from a single atom. Electrons
with sufficient energy proceed to interact with the absorbing medium identically to
beta radiation.
An important factor that distinguishes different radiation types from one
another is the Linear Energy Transfer (LET), which is the rate at which the radiation
loses energy with distance traveled through the absorber. Low LET species are
usually low mass, either photons or electron mass species (beta particles, positrons)
and interact sparsely along their path through the absorber, leading to isolated
regions of reactive radical species. High LET species are usually greater in mass
than one electron, for example particles, and lose energy rapidly resulting in a
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cluster of ionisation events in close proximity to one another. Consequently, the Radiation Chemistry
heavy particle travels a relatively short distance from its origin.

Areas containing a high concentration of reactive species following absorption
of energy from radiation are referred to as spurs. In a medium irradiated with low
LET radiation the spurs are sparsely distributed across the track and are unable to NOTES
interact. For high LET radiation the spurs can overlap, allowing for inter-spur
reactions, leading to different yields of products when compared to the same medium
irradiated with the same energy of low LET radiation.
Reduction of Organics by Solvated Electrons
A recent area of work has been the destruction of toxic organic compounds by
irradiation; after irradiation, ‘dioxins’ (polychlorodibenzo-p-dioxins) are
dechloroinated in the same way as PCBs can be converted to biphenyl an inorganic
chloride. This is because the solvated electrons react with the organic compound
to form a radical anion, which decomposes by the loss of a chloride anion. If a
deoxygenated mixture of PCBs in isopropanol or mineral oil is irradiated
with gamma rays, then the PCBs will be dechlorinated to form
inorganic chloride and biphenyl. The reaction works best in isopropanol
if potassium hydroxide (caustic potash) is added. The base deprotonates the
hydroxydimethylmethyl radical to be converted into acetone and a solvated electron,
as the result the G value (yield for a given energy due to radiation deposited in the
system) of chloride can be increased because the radiation now starts a chain
reaction, each solvated electron formed by the action of the gamma rays can now
convert more than one PCB molecule. If oxygen, acetone, nitrous oxide, sulfur
hexafluoride or nitrobenzene is present in the mixture, then the reaction rate is
reduced. This work has been done recently in the USA, often with used nuclear
fuel as the radiation source.
In addition to the work on the destruction of aryl chlorides it has been
shown that aliphatic chlorine and bromine compounds such as perchloroethylene,
Freon (1,1,2-trichloro-1,2,2-trifluoroethane) and halon-2402 (1,2-dibromo -1,1,
2,2 -tetrafluoroethane) can be dehalogenated by the action of radiation on alkaline
isopropanol solutions. Again a chain reaction has been reported.
In addition to the work on the reduction of organic compounds by irradiation,
some work on the radiation induced oxidation of organic compounds has been
reported. For instance the use of radiogenic hydrogen peroxide (formed by
irradiation) to remove sulfur from coal has been reported. In this study it was
found that the addition of manganese dioxide to the coal increased the rate of
sulfur removal.
Reduction of Metal Compounds
In addition to the reduction of organic compounds by the solvated electrons it has
been reported that upon irradiation a pertechnetate solution, at pH 4.1 is converted
to a colloid of technetium dioxide. Irradiation of a solution at pH 1.8 soluble Tc
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Material 137
Radiation Chemistry (IV) complexes are formed. Irradiation of a solution at 2.7 forms a mixture of the
colloid and the soluble Tc (IV) compounds. Gamma irradiation has been used in
the synthesis of nanoparticles of gold on iron oxide (Fe2O3).
It has been shown that the irradiation of aqueous solutions
NOTES of lead compounds leads to the formation of elemental lead, when an inorganic
solid such as bentonite and sodium formate are present then the lead is removed
from the aqueous solution.
Polymer Modification
Another key area uses radiation chemistry to modify polymers. Using radiation, it
is possible to convert monomers to polymers, to crosslink polymers, and to break
polymer chains. Both man-made and natural polymers (such as carbohydrates
can be processed in this way.
Water Chemistry
Both the harmful effects of radiation upon biological systems (induction
of cancer and acute radiation injuries) and the useful effects of radiotherapy involve
the radiation chemistry of water. The vast majority of biological molecules are
present in an aqueous medium; when water is exposed to radiation, the water
absorbs energy, and as a result forms chemically reactive species that can interact
with dissolved substances (solutes). Water is ionized to form a solvated electron and
H2O+, the H2O+ cation can react with water to form a hydrated proton (H3O+)
and a hydroxyl radical (HO.). Furthermore, the solvated electron can recombine
with the H2O+ cation to form an excited state of the water, this excited state then
decomposes to species such as hydroxyl radicals (HO.), hydrogen atoms (H.)
and oxygen atoms (O.). Finally, the solvated electron can react with solutes such
as solvated protons or oxygen molecules to form respectively hydrogen atoms
and dioxygen radical anions. The fact that oxygen changes the radiation chemistry
might be one reason why oxygenated tissues are more sensitive to irradiation than
the deoxygenated tissue at the centre of a tumor. The free radicals, such as the
hydroxyl radical, chemically modify biomolecules such as DNA, leading to damage
such as breaks in the DNA strands. Some substances can protect against radiation-
induced damage by reacting with the reactive species generated by the irradiation
of the water.
It is important to note that the reactive species generated by the radiation
can take part in following reactions, this is similar to the idea of the non-
electrochemical reactions which follow the electrochemical event which is observed
in cyclic voltammetry when a non-reversible event occurs. For example, the
SF5 radical formed by the reaction of solvated electrons and SF6 undergo further
reactions which lead to the formation of hydrogen fluoride and sulfuric acid.
In water the dimerisation reaction of hydroxyl radicals can form hydrogen
peroxide, in saline systems the reaction of the hydroxyl radicals with chloride anions
form hypochlorite anions.
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It has been suggested that the action of radiation upon underground water is Radiation Chemistry
responsible for the formation of hydrogen which was converted by bacteria

into methane. A series of papers on the subject of bacteria living under the surface
of the earth which are fed by the hydrogen generated by the radiolysis of water
can be read on line. NOTES
Chemosensor
The SAW chemosensor is non-ionic and nonspecific. It directly measures the total
mass of each chemical compound as it exits the gas chromatography column and
condenses on the crystal surface, thus causing a change in the fundamental acoustic
frequency of the crystal. Odor concentration is directly measured with this
integrating type of detector. Column flux is obtained from a microprocessor that
continuously calculates the derivative of the SAW frequency.
This is the branch of science which involves the study of chemical effects
induced by ionizing radiations like X-rays, -rays, electrons, protons, -particles
and neutrons. This is similar to photochemistry with a slight difference in a absorption
process.
Comparison with Photochemistry: Radiation chemistry differs from
photochemistry in the following respects:
 In case of photochemistry, the absorption process is more complicated.
Here the radiation is usually monochromatic, whereas the radiations in
radiation chemistry may or may not be monochromatic.
 In photochemistry one molecule absorbs one photon which at least initially
produces excited state, but in case of radiation chemistry, the absorption
process passes through a spectrum of lower energy states. Thus, many
other molecules are ionized or excited by the initial quanta or particles.
 The absorption in photochemistry is purely and highly specific even in dilute
solutions. The radiations are absorbed by the solute, where as in radiation
chemistry, the radiations of all energies may be absorbed by both solute
and the solvent as well.
 In photochemistry, the excited states produced by absorption are distributed
homogeneously in the system. The radiation chemistry involves the presence
of uncharged species like radicals and atoms rather than ions, produced in
the primary reactions.
A quantitative measure of these radiation induced effects is given by a quantity
called G value of a reaction. It is defined as the number of molecules reacting per
100 electron volts of energy absorbed. This definition may be expressed in slightly
different manner. Since, the absorption of 1 electron volt by a molecule is equivalent
to N electron volts per mole where N is Avagadro’s number and if e is the electronic
charge, then Ne will be equal to one Faraday or 96,500 coulombs. Hence N
electron volts is equivalent to 96,00 volt coulombs or 23,06 cal. Hence, G value
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Material 139
Radiation Chemistry gives the number of moles reacting per 2,306 kcal of energy absorbed. In actual
practice G is a small number. Only a few moles react for the absorption of over
2000 kcal of energy from the radiation, whereas chemical reactions require about
50 kcal per mole. Thus, only a small part of the radiation absorbed is utilized for
NOTES chemical reactions and most of it is absorbed as heat. The decomposition of water
by radiation, has been studied in detail, though the reaction mechanism has not
been definitely established. The earliest detectable products are hydrogen and
hydrogen peroxide and transient reactive species with properties to be expected
from H atoms and OH radicals.
The reaction may be represented as
H2O  Ions and excited molecules  H + OH
The symbol  is used to represent the absorption of ionizing radiation. The
other reactions are
H + H  H2
OH + OH  H2O2
There is also possibility that H2 and H2 O2 are formed directly from two
molecules of water. There are large number of possible paths this simple reaction
can proceed. The calculation of G value for each probable step and the overall G
value is compared with the experimental G value. This helps us to establish the
path of a reaction.
Application of Radiation Chemistry
The applications of this fascinating field range far and wide. Following are the
main uses of radiation chemistry:
 To study reaction mechanism by radiolysis of solids, gases and liquids.
 Nitrogen fixation.
 Polymerization.
 Food-preservation.
 Sterilization.
 Production of detergents.
 Production of gammaxane ethyl bromides.
 Gamma-gardens.
 For medical purposes.
 To study the different locks.
Uses of Radiation
One use of radiation is in dating fossils, or any specimen that you want to find the
age of. The half life is the time required for half of the nuclei in a specific element to
undergo radioactive decay.
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Fission reactions refer to the splitting of an atomic nucleus into approximately Radiation Chemistry
equal parts with a release of energy. Each subsequent nuclei that results can continue
to be split in a type of ‘fission chain reaction’, generating a great amount of energy.
This is precisely how nuclear power plants generate a large amount of energy.
About 15-20% of the world’s energy comes from these nuclear power plants. NOTES
Fusion reactions refer to reactions where multiple nuclei, combine to form a heavier
nucleus (the opposite of fission reactions). The sun and stars undergo fusion
reactions.
Also, irradiation of food by gamma rays from certain isotopes also increases
shelf life of the food. For instance, irradiation of milk gives it a shelf life of three
months without refrigeration.
Dangers of Radiation
Radiation can ionize atoms in our tissues, and cause reactions similar to
decomposition or combustion in our skin. For instance, radiation can mutate
nucleotide sequences in our DNA, potentially causing cancer.
The dangers of the specific type of radiation- alpha, beta or gamma- depend
on each of their penetrative abilities. Alpha particles are not very dangerous because
they cannot penetrate the barrier of the skin. Beta particles can penetrate about
one centimeter deep in our skin. The most dangerous are gamma rays, which can
penetrate through the skin very effectively.
Units called REMs are used to measure the effective biological damage that
radiation causes. Some natural sources of radiation include cosmic radiation, the
earth’s radiation, and even the radiation from elements found naturally in human
tissue. Medical sources of radiation include X-rays, and radiotherapy, for instance
in cancer treatment. Artificial sources of radiation include the nuclear power industry,
and fallout from nuclear tests. However, the average exposure for an individual
with all of these sources combined is only about 0.2 REMs/year.
Check Your Progress

1. What is radiation chemistry?
2. How isotopes are different forms of element ?
3. Define binding energy.
4. Which law is applied in the radioactive reaction?
5. How many types of nuclear reactions are there?
7.3 RADIOLYSIS OF WATER

Water radiolysis is the decomposition of water molecules when they are irradiated
by ionising radiation. Water molecules are decomposed to form radiolysis products:
ions, excited molecules and free radicals are the first reactive species formed. Self-Instructional
Material 141
Radiation Chemistry While both ions and excited molecules can give stable chemical products directly,
the free radicals are unstable with high reactivity. Therefore, most of them only
exist during the intermediated formation, and eventually disappear in the water. In
general, the reaction of water radiolysis can be written as Equation 1. Due to
NOTES ionizing radiation, the radiolysis of water produces: hydrated electrons, H• atoms,
HO• and HO•2 radicals, H3O+ and OH” ions, H2 (dihydrogen) and H2O2 (hydrogen
peroxide) molecules. The global equation of water radiolysis is now well understood
experimentally as well as theoretically.
(1)
Mechanism of Water Radiolysis
Ionising radiation produces ionisation and excitation by transferring energy to
electrons present in water molecules. The energy is first absorbed, and then
deposited into water molecules. During the initial interaction, inner-shell electrons
may be excited and the absorbed energy is rapidly redistributed. Thus, chemically
important ions and excited states are produced by loss or excitation of less-firmly
bound electrons, such as the outer-shell electrons.
One of the recent models about the mechanism of water radiolysis was proposed
by Sxiatla-Wojcik and Buxton , shown in Figure 7.1. It divides the water radiolysis
mainly into three steps:
 The Physical Stage
 The Physico-Chemical Stage
 The Chemical Stage
Fig. 7.1 Schematic Diagrams of Water Radiolysis

As shown in the Figure 7.1, it illustrates the water decomposition as a function of
time after the irradiation. Precisely, it shows the chemical reactions have been
taken place during the first 1s after the radiation energy deposited into the water
molecules.
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Radiation Chemistry
NOTES
Fig. 7.2 Radiolysis of Intracellular Water (H20)

The above Figure 7.2 illustartes the exposure of cells to ionizing radiation induces
high-energy radiolysis of H2O water molecules into H+ and OH- radicals. These
radicals are themselves chemically reactive, and in turn recombine to produce a
series of highly reactive combinations, such as superoxide (HO 2)
and peroxide (H2O2) that produce oxidative damage to molecules within the cell.
The Physical Stage
The physical stage is the absorption of ionising radiation by water, which leads the
ionisation and excitation of water molecules. Therefore, the incident particles and
the electrons in water molecules are generated and both slowed down. It is the
period that consists of energy deposition followed by fast relaxation processes.
The physical stage is the first step of water radiolysis, which only lasts about
10–15 s.
The water molecule H2O can either be ionised, by removing an electron, Equation
2:
(2)
(3)
or be excited, by transferring an electron from a fundamental state to an excited
state, Equation 4 :
(4)
(5) Self-Instructional
Material 143
Radiation Chemistry Nevertheless, Equations 3and 5 are considered as the continuous reactions of
water molecule and the ejected electron. At the end of this stage, the reactions
have formed: excited water molecules H2O+ , ionised water molecules H2O+ and
sub-excitations electrons e–.
NOTES
The Physico-Chemical Stage
The physico-chemical stage is the second step of water radiolysis, from 10–15s to
10–12 s, in which a thermal equilibrium is established. During this period, the ionised
and excited water molecules undergo transformations and thus they dissipate energy
by transferring it to their neighbouring molecules and breaking bonds. In the mean
time, the sub - excitations electrons become thermalised and then subsequently
hydrated. There are many different processes in this stage and not all of them have
been well characterised experimentally. However, some important processes are
well detailed which will be represented in the following sections.
Excited Water Molecules H2O+
Dissociative relaxation The dissociation of the excited water molecule H2O+
produces the radicals HO• and H• by bond breaking, Equation 6. Two models
have been described in the literature. One leads to dihydrogen molecule H2 and O
(1D) which can react quickly with water molecule and give the OH• radical. In the
second model, the H• radical and O (3P) can be formed by the reaction below, but
due to the weak quantity in the liquid water, this reaction is often negligible, That is
the reason for its absence in the scheme of main reactions . It is worth mentioning
that O (1D) and O (3P) are the singlet and triplet state of the atomic oxygen
respectively. It needs to be pointed out that the excited water molecule can return
to its fundamental state without any dissociation, but only by losing heat. In the
case of liquid water, the role of excited molecules is normally less important
compared to the ionised ones.
(6)
(7)
(8)
Ionized Water Molecules H2O+
Ion-molecule reaction The ion-molecule reaction can also be thought as transferring
a proton to a neighbouring molecule. The ion H2O+ is not stable and it reacts very
quickly with water molecules, Equation 9. This reaction is important because it
leads to the production of HO• radical and proton H3O+, which may have other
role in further reactions
(9)
–
Sub-Excitation Electrons e
Thermalisation and solavatation of sub-excitation electrons Most ejected electrons
have low energy. However, some of them may have considerable energy during
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144 Material
collisions with other molecules before the electron neutralises a positive ion. In Radiation Chemistry
other words, the electrons is reduced to thermal or near thermal energy before
recombination occurs, Equation 2.27. Then it can interact with the surrounding
water molecules and eventually becomes an hydrated electron, e–aq, Equation 10.
The energy of thermalization is about 0.0025 eV at 25°C. NOTES
(10)
(11)
Germinate recombination The germinate recombination process is an ion
recombination. The energy is lost during molecular collisions and the molecule
rapidly drops to its lowest excited state, Equation 11. During the ionisation of the
water molecules, the potential is about 8 eV. The incident particle or the
electromagnetic radiation can have a sufficient energy to eject an electron which
can recombine with a neighbouring water molecule, a positive water ion, in order
to give an excited water molecule.
(12)
Dissociative electron attachment (DEA) Before the thermalization, apart from the
recombination process, the sub-excitation electrons can also react with a water
molecule by giving the H2, HO• and OH”, Equations 13 and 14. This process is
thus called dissociative electron attachment. It involves the resonant capture of e–
to a water molecule followed by the dissociation of the transient anion and by
reaction of the hydride anion with another water molecule through a prompt proton
transfer process. The electron capture by this process may lead to a
disproportionately high rate of decomposition.
(13)
(14)
After 1 ps of the energy deposition into water molecules, which is also the end of
the physicochemical stage, the spatial distribution around the axis of the ionisation
track includes e–aq, H3O+ and HO• which are the species involving in the reactions
for the next stage. The species H2 and H2O2 are also created in this stage. All these
species are referred as the initial yields of water radiolysis.
The Chemical Stage
The chemical stage is often considered as highly non-homogeneous, and hence in
some literature, it is named as the non-homogeneous chemical stage. However,
one thing can be sure that the chemical stage starts with a non-homogeneous state
and ends homogeneously. It takes place between 10–12 and 10–6 s. The radical
species react in the tracks and then diffuse in solution. They can thus react with
each other and also with surrounding molecules in the solution, Equations 15, 16
and 17.
(15)
(16)
(17)
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Material 145
Radiation Chemistry In general, this stage can be divided into two: the heterogeneous and the
homogeneous ones. At the heterogeneous chemical stage, normally extends from
10"11 to 10"8 s, the recombination reactions are favoured which lead to the formation
of molecular products in a relative high concentration in small zones along the
NOTES radiation track. Afterwards, the track of the particles expands because of the
diffusion of radicals and their subsequent chemical reactions. Therefore, it brings
the homogeneous state of the radicals and molecules to the solution at the end of
the chemical stage.
1 µs after the particles pass through, the distribution of radiolyic species in
water is considered homogeneous. The reactions occur after these three stage can
generally be well described homogeneously while all the species have diffused
evenly into the water.
Some Significant Points
 The oxygen is not a primary product of water radiolysis, it is formed in the
stage of homogeneous chemistry which means after 10–6 s of energy
deposition in the water.
 The radical superoxide, OH•2 , is presented like a primary product in the
global equation, but actually it is formed in the heterogeneous stage and the
mechanism of its formation is not clear yet. The most cited hypothesis is that
it is formed by the reaction between HO• radical and an oxygen atom at
triplet state.
 The formation of molecular hydrogen H2 is involved in two stages after the
initial energy disposition: it can be produced in the chemical stage. In the
earlier physicochemical stage, the formation of H2 can be presented by the
dissociation of excited water molecules, and the dissociative electron
attachment. Indeed, the dominant way of H2 formation is the dissociative
recombination process of the water cation and the non-hydrated electron
during the physicochemical stage, not in the last stage.
 The production of H2 has two different types of tracks along the radiation
path, either are spherical spurs formed at more than 100 nm separations
with low LET radiation, or are cylindrical track of connecting spurs with
high LET radiation.
Radiolytic Yields
The radiolytic yield, noted as g(X), is defined as the number of species created or
destroyed for 100 eV deposited energy. SI unit for the radiolytic yield is mol.J–1
which equals to 9.649 × 106 molecules/100 eV. It can measure the radicals and
molecular products that escape from the spurs and tracks. Actually, there is a
competition between the diffusion and the reaction of these species as the non-
homogeneous concentration gradients relax. However, these yields are usually
referred to as homogeneous or steady-state yields, and they are representative of
the state of an electron track as found at about 10–7 s 9 , after the passage of an
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146 Material
ionising particle which has deposited energy in the system. It means that any Radiation Chemistry
reactions occurring within spurs and tracks have been completed.

The primary yields of both radical (e–aq, H• , OH• , OH• 2 ) and molecular
(H2, H2O2) products can be simply subdivided into two groups: the reducing
radicals e– and H• , and the oxidising products OH• , HO• 2 and H2O2. The NOTES
molecular hydrogen is relatively inert and normally plays little part in the subsequent
reactions.
To maintain a material balance, the relationship between the radical and
molecular yields are written as the equations (Equations 18, 19 and 20) below, in
which g(-H2O) is defined as the corresponding yield of decomposition of water at
this stage.
Oxygen Part (18)
Hydrogen Part
(19)
Charges Conservation
(20)
With the three precise equations, we can establish the relation of all the primary
products:
(21)
The equation expressed in Equation 21 is often used in the determination of
radiolytic yields. The first thing to point out is that all the radiolytic yields evolute
with time, illustrated in Figure 7.3. It indicates that the radicals yields decrease
while the molecular yields increase as a function of time. In other words, it means
that the radicals recombine and form molecular products with time. Therefore, the
radicals are difficult to detect after a short time of the radiation.
Fig. 7.3 Time-Dependent of Primary Yields Self-Instructional

Material 147
Radiation Chemistry The above Figure 7.2 shows the time-dependent of primary yields; H• , HO• , H2,
H2O2 and e–aq produced by low LET radiation tracks of proton (300 MeV, LET
<“ 0.3 keV/µm) at neutral pH and 25°C. Broken line: IONLYS-IRT calculation;
solid line: SBS calculation; spline: Monte-Carlo simulation results
NOTES In general, the radiation types do not have a huge influence on the radiolytic
yields, especially for low LET radiations. Nevertheless, for LET > 10 keV/µm,
g(H• ) increases as the incident ion velocity increases. The radiolytic yields still
depend on a lot of parameters: the characteristics of irradiation, such as LET and
dose rate; the characteristics of water itself, like temperature, pressure and pH.
Influence of LET
The Linear Energy Transfer LET of incident radiation can significantly change the
values of primary radiolytic yields. The radiation tracks can be very differently due
to the LET, low LET gives isolated spurs and high LET gives cylindrical tracks.
Therefore, different tracks cause different diffusion models for the primary yields.
The radicals H• and HO• in cylindrical tracks are easier to combine with each
other because they are closer in distance and more concentrated than in spurs,
then result in form more molecular products. On the contrary, spurs are favoured
to form more radical products. In short, with the increase of LET, the yields of
radical products (e–aq, H• , HO• ) decrease while the molecular yields (H2O2 and
H2) increase. However, for H• yields, it reaches a maximum value around 6-10
keV/µm and then decreases with LET at neutral pH and 25°C. The yields of O2,
not shown in the figure, actually, increase significantly with LET at the similar
conditions,
Influence of pH
The pH influence has been studied for a long time, as Draganić and Draganić
conclude, which I quote: There is no strong dependence of the primary yields on
pH, although the situation at extreme pH’s is not yet quite clear. Therefore, we
consider that the radiolytic yields are not affected by the pH between 4 and 9.
Furthermore, even for the time less than 10–6 s after energy deposition, pH can
also be regarded as no large influence on the radiolytic yields ranging form 1 to
13.
When pH is higher than 9, the primary yields are also affected. However, for
alkaline solutions, the evolution of the primary yields is still not very clear yet.
However, under basic condition, they are most influenced by the radical O–.The
most cited explanation is that the yields of H2O2 and e–aq + H• decrease while
g(HO• ) increase as the pH increase from 12 to 14. However, there is an inverse
explanation of the primary yields due to the selection of the constant reaction rate
of the radical O–.
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Radiation Chemistry
NOTES
Fig. 7.4 Steady-state Concentration of Oxide Species as Function of the Square Root of
Dose Rate: [H2O2]+2[O2]; •: [H2O2].
Check Your Progress

6. What is water radiolysis?
7. In how many stages water radiolysis divided?
8. What is physical stage of water radiolysis?
9. What happens in physico-chemical stage of water radiolysis
7.4 PULSED RADIOLYSIS

Pulse Radiolysis is a technique of exposing a sample of material to a beam of
highly accelerated electrons to initiate fast reaction events occurring between 10-
11 and 102 s after energy absorption.
The technique is used to study fast
reactions of biologically
important molecules, or example,
the kinetics and thermodynamics
of redox processes and electron-
transfer reactions, enzymatic processes
and structural effects which are
revealed by physical or kinetic
properties.
In other words we can say that it is an
end station for ultrafast pulse radiolysis
using laser-driven secondary radiation
sources is being developed at ELI-
Beamlines. Temporal resolution of tens of femtoseconds will be made possible,
pushing far below the famous ‘picosecond barrier’ in radiolysis and experimentally
revealing the time scales where primary radical products are generated from the
interactions of ionizing radiation with matter.
In the scientific field of radiation chemistry, the chemical effects of ionizing
radiation of matter are studied to advance our knowledge both in fundamental
atomic and molecular science and in applied radiation methods. In the latter case,
research in radiation chemistry has strong connections to areas that study and Self-Instructional
Material 149
Radiation Chemistry employ radiation effects in living systems, with important medical applications in
radiotherapy and radiation dosimetry, and also with areas dealing with the
development of applied radiation processing methods, such as radiation sterilization,
radiation sanitation, radiation polymerization, and food irradiation.
NOTES
Pulse radiolysis is an experimental research method that has helped more
than any other method in working toward an understanding of the underlying rapid
chemical and physico-chemical processes that follow the absorption of ionizing
radiation in matter and are ultimately responsible for the final observable effects.
The basic principle of this method is that it uses a very short radiation pulse of
ionizing radiation and then detects the resulting chemical changes with high time
resolution. Since the characteristic time of most radiation-chemical processes is
considerably shorter than 1 millisecond (10–3s), human observation needs to rely
on scientific instruments with high time resolution. Currently established methods
for pulse radiolysis employ laser-photocathode radiofrequency linear accelerators
(LINAC) to generate ultrashort pulses of electrons, routinely achieving time
resolution of several picoseconds and in some cases resolving the sub-picosecond
(< 10-12 s) temporal region.
The ELI-Beamlines facility will be capable of producing multiple kinds of
pulsed ionizing radiation generated by direct laser-plasma interaction in matter
(soft and hard X-rays, electrons, or protons and possibly even heavier ions). When
compared to accelerators, these laser-driven radiation sources offer two principle
advantages for applications in the area of pulse radiolysis:
 The short length of the duration of the pump radiation pulse (~ 10-14s),
 Near-perfect synchronization of the temporal overlap of the radiation pulse
and the laser probe (low jitter).
The first advantage results from the original ultrashort duration of the laser
pulses that is provided by the modern Ti:Sapphire laser oscillator technology
coupled with Optical Parametric Chirped-Pulse Amplification (OPCPA), which is
capable of delivering high-power impulses measuring down to several
femtoseconds. The second advantage stems from the use of one original laser
impulse for driving the pump radiation pulse and operating the inspecting laser
probe pulse; this greatly reduces the demanding problem of synchronization jitter
that contributes to the challenges of overcoming the ‘picosecond barrier’ in pulse
radiolysis experiments using Radio Frequency (RF) LINAC-based electron
accelerators.
Check Your Progress

10. What is pulse radiolysis?
11. Where is pulse radiolysis technique used?
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Radiation Chemistry
QUESTIONS
1. Radiation chemistry involves the study of nuclear reactions. There are clear NOTES
differences between a chemical reaction, and a nuclear reaction, a chemical
reaction involves electrons of an atom (which orbit the nucleus), while a
nuclear reaction involves a reaction within the nucleus of an atom (which
consists of protons and neutrons).
2. Isotopes are different forms of an element which contain the same number
of protons as the element on the periodic table, but each isotope of the
element contains a different number of neutrons (thus isotopes have varying
mass numbers).
3. A great amount of energy holds the nucleus together, in a nuclear reaction,
a great amount of energy is released as the nucleus is disintegrated: this
energy is called the binding energy.
4. It is important to note that in a radioactive reaction, and in almost all the
reactions, the law of conservation of mass applies, which means that the
total mass before the reaction has to equal the total mass after the reaction
occurs.
5. There are three primary types of nuclear reactions:
 Alpha Radiation
 Beta Radiation
 Gamma Radiation
6. Water radiolysis is the decomposition of water molecules when they are
irradiated by ionising radiation.
7. Water radiolysis is divided in three steps:
 The Physical Stage
 The Physico-Chemical Stage
 The Chemical Stage
8. The physical stage is the absorption of ionising radiation by water, which
leads the ionisation and excitation of water molecules.
9. The physico-chemical stage is the second step of water radiolysis, from
10–15 to 10–12 s, in which a thermal equilibrium is established.
10. Pulse Radiolysis is a technique of exposing a sample of material to a beam of
highly accelerated electrons to initiate fast reaction events occurring between
10-11 and 102 s after energy absorption.
11. The pulse radiolysis technique is used to study fast reactions of biologically
important molecules, or example, the kinetics and thermodynamics
of redox processes and electron-transfer reactions, enzymatic processes and
structural effects which are revealed by physical or kinetic properties.
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Material 151
Radiation Chemistry
7.6 SUMMARY
 Radiation chemistry involves the study of nuclear reactions. There are clear
NOTES differences between a chemical reaction, and a nuclear reaction, a chemical
reaction involves electrons of an atom (which orbit the nucleus), while a
nuclear reaction involves a reaction within the nucleus of an atom (which
consists of protons and neutrons).
 Marie Curie discovered radioactivity, which is the spontaneous disintegration
of the unstable nuclei of some elements, or isotopes of elements, into more
stable nuclei.
 Isotopes are different forms of an element which contain the same number
of protons as the element on the periodic table, but each isotope of the
element contains a different number of neutrons (thus isotopes have varying
mass numbers).
 The radical species then proceed to react with each other or with other
molecules in their vicinity. It is the reactions of the radical species that are
responsible for the changes observed following irradiation of a chemical
system.
 Charged radiation species Interact through Coulombic forces between the
charges of the electrons in the absorbing medium and the charged radiation
particle. These interactions occur continuously along the path of the incident
particle until the kinetic energy of the particle is sufficiently depleted.
 Uncharged species (g photons, x-rays) undergo a single event per photon,
totally consuming the energy of the photon and leading to the ejection of an
electron from a single atom. Electrons with sufficient energy proceed to
interact with the absorbing medium identically to beta radiation.
 Areas containing a high concentration of reactive species following absorption
of energy from radiation are referred to as spurs. In a medium irradiated
with low LET radiation the spurs are sparsely distributed across the track
and are unable to interact.
 For high LET radiation the spurs can overlap, allowing for inter-spur
reactions, leading to different yields of products when compared to the
same medium irradiated with the same energy of low LET radiation.
 Water radiolysis is the decomposition of water molecules when they are
irradiated by ionising radiation. Water molecules are decomposed to form
radiolysis products: ions, excited molecules and free radicals are the first
reactive species formed.
 Ionising radiation produces ionisation and excitation by transferring energy
to electrons present in water molecules. The energy is first absorbed, and
then deposited into water molecules.
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152 Material
 The physical stage is the absorption of ionising radiation by water, which Radiation Chemistry
leads the ionisation and excitation of water molecules. Therefore, the incident
particles and the electrons in water molecules are generated and both slowed
down.
NOTES
 The H• radical and O (3P) can be formed by the reaction below, but due to
the weak quantity in the liquid water, this reaction is often negligible, That is
the reason for its absence in the scheme of main reactions .
 The O (1D) and O (3P) are the singlet and triplet state of the atomic oxygen
respectively. It needs to be pointed out that the excited water molecule can
return to its fundamental state without any dissociation, but only by losing
heat.
 Pulse radiolysis is an experimental research method that has helped more
than any other method in working toward an understanding of the underlying
rapid chemical and physico-chemical processes that follow the absorption
of ionizing radiation in matter and are ultimately responsible for the final
observable effects.
 The basic principle of this method is that it uses a very short radiation pulse
of ionizing radiation and then detects the resulting chemical changes with
high time resolution. Since the characteristic time of most radiation-chemical
processes is considerably shorter than 1 millisecond (10-3 s), human
observation needs to rely on scientific instruments with high time resolution.
 Currently established methods for pulse radiolysis employ laser-
photocathode radiofrequency linear accelerators (LINAC) to generate
ultrashort pulses of electrons, routinely achieving time resolution of several
picoseconds and in some cases resolving the sub-picosecond (< 10-12 s)
temporal region.
7.7 KEY WORDS
 Radiation chemistry: Radiation chemistry involves the study of nuclear

reactions
 Binding energy: A great amount of energy holds the nucleus together, in a
nuclear reaction, a great amount of energy is released as the nucleus is
disintegrated: this energy is called the binding energy.
 Water radiolysis: Water radiolysis is the decomposition of water molecules
when they are irradiated by ionising radiation.
 Physical stage: The physical stage is the absorption of ionising radiation
by water, which leads the ionisation and excitation of water molecules.
 Physico-chemical stage: The physico-chemical stage is the second step
of water radiolysis, from 10–15 to 10–12 s, in which a thermal equilibrium is
established. Self-Instructional
Material 153
Radiation Chemistry  Pulse radiolysis: Pulse Radiolysis is a technique of exposing a sample
of material to a beam of highly accelerated electrons to initiate fast reaction
events.
NOTES
EXERCISES

1. Give a brief note on radiation chemistry.
2. What is radiolysis?
3. Write short notes on:
i. Alpha Decay
ii. Beta Decay
iii. Gamma Radiation
4. Brief a note om reduction of organics by solvated electrons.
5. Give short note on water chemistry.
6. List some of the uses of radiation.
1. Explain the radiation interactions with matter
2. Elaborate a detailed note on radiolysis of water.
3. Discuss about the physical stage, physico-chemical stage and the chemical
stage in detail.
4. Give a well labelled diagram of radiolysis of intracellular water (H20).
5. Write in detail about radiolytic yields.
6. Explain the influence of pH in water radiolysis.
7. Give detailed account on pulse radiolysis.

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154 Material
Fundamentals of
Polymers
BLOCK - III
POLYMER CHEMISTRY
NOTES
UNIT 8 FUNDAMENTALS OF
POLYMERS
Structure
8.0 Introduction
8.1 Objectives
8.2 Polymers-Addition Polymerization: Definition and Classification
8.3 Initiators: Types and Initiator Efficiency
8.5 Summary
8.6 Key Words
8.0 INTRODUCTION
Prior to the early 1920’s, chemists doubted the existence of molecules having
molecular weights greater than a few thousand. This limiting view was challenged
by Hermann Staudinger, a German chemist with experience in studying natural
compounds such as rubber and cellulose. In contrast to the prevailing rationalization
of these substances as aggregates of small molecules, Staudinger proposed they
were made up of macromolecules composed of 10,000 or more atoms. He
formulated a polymeric structure for rubber, based on a repeating isoprene unit
(referred to as a monomer). For his contributions to chemistry, Staudinger received
the 1953 Nobel Prize. The terms polymer and monomer were derived from the
Greek roots poly (many), mono (one) and meros (part).
Recognition that polymeric macromolecules make up many important natural
materials was followed by the creation of synthetic analogs having a variety of
properties. Indeed, applications of these materials as fibers, flexible films, adhesives,
resistant paints and tough but light solids have transformed modern society. Some
important examples of these substances are discussed in the following sections.
In polymer chemistry, polymerization is a process of reacting monomer
molecules together in a chemical reaction to form polymer chains or three-
dimensional networks. There are many forms of polymerization and different
systems exist to categorize them.
In this unit, you will study about polymerization , polymers-addition
polymerization its definition and classification and type of initiators and initiator
efficiency in detail. Self-Instructional
Material 155
Fundamentals of
Polymers 8.1 OBJECTIVES
NOTES  Understand what polymerization is
 Expalin polymers-addition polymerization its definition and classification
 Discuss the type of initiators and initiator efficiency
8.2 POLYMERS-ADDITION POLYMERIZATION:

DEFINITION AND CLASSIFICATION
Polymerization, is a process in which relatively small molecules, called monomers,
combine chemically to produce a very large chain like or network molecule, called
a polymer. The monomer molecules may be all alike, or they may represent two,
three, or more different compounds. Usually at least 100 monomer molecules
must be combined to make a product that has certain unique physical properties,
such as, elasticity, high tensile strength, or the ability to form fibres, that differentiate
polymers from substances composed of smaller and simpler molecules; often,
many thousands of monomer units are incorporated in a single molecule of a polymer.
The formation of stable covalent chemical bonds between the monomers sets
polymerization apart from other processes, such as crystallization, in which large
numbers of molecules aggregate under the influence of weak intermolecular forces.
Two classes of polymerization usually are distinguished:
 Condensation Polymerization
 Addition Polymerization
In condensation polymerization, each step of the process is accompanied by
the formation of a molecule of some simple compound, often water. In addition
polymerization, monomers react to form a polymer without the formation of by-
products.
Addition polymerization usually are carried out in the presence of catalysts,
which in certain cases exert control over structural details that have important
effects on the properties of the polymer.
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156 Material
Linear Polymers, which are composed of chainlike molecules, may be Fundamentals of
Polymers
viscous liquids or solids with varying degrees of crystallinity; a number of them
can be dissolved in certain liquids, and they soften or melt upon heating. Cross-
linked polymers, in which the molecular structure is a network, are
thermosetting resins (i.e., they form under the influence of heat but, once formed, NOTES
do not melt or soften upon reheating) that do not dissolve in solvents. Both linear
and cross-linked polymers can be made by either addition or condensation
polymerization.
Polymerization - Addition Polymers
Polymers are very different from the other kinds of organic molecules that you
have seen so far. Whereas other compounds are of relatively low molar mass,
polymers are giant molecules of very high molar mass. Polymers are the primary
components of all sorts of plastics and related compounds. A polymer is a large
molecule formed of many smaller molecules covalently bonded in a repeating pattern.
The small molecules which make up the polymer are called monomers. Polymers
generally form either from an addition reaction or a condensation reaction.
Addition Polymers
An addition polymer is a polymer formed by chain addition reactions between
monomers that contain a double bond. Molecules of ethene can polymerize with
each other under the right conditions to form the polymer called polyethylene.
nCH2=CH2=(CH2CH2)n
The letter n stands for the number of monomers that are joined in repeated
fashion to make the polymer and can have a value in the hundreds or even
thousands.
Fig. 8.2 Polyethylene Synthesis

The reactions above show the basic steps to form an addition polymer.
1. Initiation: A free radical initiator (X*) attacks the carbon-carbon double
bond (first step above). The initiator can be something like hydrogen
peroxide. This material can easily split to form two species with a free electron
attached to each: H–O–O–H2H–O. This free radical attacks a carbon-
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Material 157
Fundamentals of carbon double bond. One of the pi electrons forms a single bond with the
Polymers
initiator while the other pi electron forms a new free radical on the carbon
atom.
2. Propagation: The new free radical compound interacts with another alkane,
NOTES continuing the process of chain growth (second step above).
3. Termination: It occurs whenever two free radicals come in contact with
one another (not shown). The two free electrons form a covalent bond and
the free radical on each molecule no longer exists.
Polyethylene can have different properties depending on the length of the
polymer chains and on how efficiently they pack together. Some common
products made from different forms of polyethylene include plastic bottles,
plastic bags, and harder plastic objects such as milk crates.
Several other kinds of unsaturated monomers can be polymerized and are
components in common household products. Polypropylene is stiffer than
polyethylene and is in plastic utensils and some other types of containers.
Fig. 8.3 Polypropylene Structure

Polystyrene is used in insulation and in molded items such as coffee cups.
Fig. 8.4 Polystyrene Synthesis and Structure

Polyvinyl Chloride (PVC) is extensively used for plumbing pipes
Fig. 8.5 Polyvinyl Chloride

Polyisoprene is a polymer of isoprene and is better known as rubber. It is produced
naturally by rubber trees, but several variants have been developed which
demonstrate improvements on the properties of natural rubber.
Fig. 8.6 Polyisoprene

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158 Material
Polymers are one of the most important products, which find an important place in Fundamentals of
Polymers
every walk of modern civilisation. The term polymer (Greak word: poly + meros,
means, many parts) denotes a molecule produced by the repetition of some simpler
unit, called the mer or the monomer.
NOTES
The term macromolecule (big molecule) is also often used to cover the
large molecule of complex structure. A naturally occurring macromolecule is insulin,
a protein hormone, which occurs in the pancreas, and is best known agent to
lower blood sugar in diabetic patients. It has the repeating units with amide linkages,
i.e.,
R O
| |
(—CH—O—C—NH—)n, where n = 51 and R has sixteen variations.
The science of macromolecules is divided between biological and non-biological
materials, each having vital importance in our daily life. Biological polymers, i.e.,
proteins, nucleic acids (DNA, RNA), starch, cellulose and enzymes are complex
macro molecules form the very foundation of life and intelligence and provide
much of the food for the existance of man. This chapter however, is concerned
mainly with the chemistry of some polymers. These are primarily the synthetic
materials used for plastics, fibres, and elastomers and a few naturally occurring
polymers, such as rubber, wool and cellulose. The polymers are truly indispensible
to mankind, as they are used to meet the basic needs-clothing, shelter,
communication, and transportation, as well as to the conveniences of modern
living.
The name of a polymer is usually derived from the name of the monomer
(repeat unit) by prefixing the word poly to it. To illustrate the polymerization product
of ethylene is known as polyethylene and that of sytrene is called polystyrene. The
number of repeating units in the chain is called the Degree of Polymerization (DP)
and specifies the length of the chain. Degree of polymerization is denoted by the
letter n or P. The molecular weight of the polymer is the product of the molecular
weight of the repeat unit and the degree of polymerization, i.e.,
Mpoly = n × Mm
or
M poly (mol. wt. of polymer)
n (Degree of polymerization) =
M m (mol. wt. of repeat unit)
The degree of polymerization may vary over a wide range, i.e., from a few
units to 10,000 and even more. Polymers with high P are called high polymers and
are mostly useful for plastics, rubbers or fibres, etc., while those with low P are
known as oligomers.
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Material 159
Fundamentals of Classification of Polymers
Polymers
A polymer may consist of monomers of identical or of different chemical structure.
If it has identical units then it is known as homopolymer, whereas a polymer
NOTES containing several types of monomeric units in its chain is known as copolymer, or
mixed polymer. In some cases the repetition is linear and a chain is built up from its
links. However, in cases the chains are branched or interconnected, to form three
dimensional structures.
Copolymers may also be linear, branched or three-dimensional. The

monomer residues, in co-polymer molecules may be arranged in the chain regularly
or at random, according to the law of chance. Copolymers of the former group
are called regular-copolymers and those of latter type, statistical or irregular
copolymers.
Copolymers with long sequence of two monomers can have two
arrangements of long chains:
1. linear copolymers in which the units of each type form fairly continuous
sequence (blocks) is known as block copolymers.
2. Branched copolymer, with monomer of one kind grafted into a backbone
of the second monomer type is termed as graft copolymer.
According to the structure of main chain, all polymers are classified into
homochain and heterochain polymers. Homochain polymers contain the chains
composed of atoms of the same element, for example, carbon, sulphur phosphorus
etc.
In heterochain polymers, the main chain is made up of atoms of different
species, for example,
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Fundamentals of
Polymers
NOTES
On the basis of chemical composition, the polymers can also be classified
as:
1. Organic Polymers: Organic polymers include compounds containing
carbon hydrogen, oxygen nitrogen, sulphur and halogen atoms. Oxygen,
nitrogen or sulphur may also be present in the backbone chain.
2. Elemento-Organic (Hetero-Organic) Polymers: These include the
following classes:
 Compounds containing carbon atoms and hetero atoms (except
for nitrogen, sulphur and oxygen atoms) in their chains.
 Compounds with inorganic chains if they contain side groups
with carbon atoms connected directly to the chain.
(iii) Compounds having carbon atoms in the main chain and hetero-
atoms (except for nitrogen, sulphur, oxygen and halogen atoms)
in side groups connected directly to the carbon atoms of the
chain. For example, polysiloxanes, polytitanoxanes, etc.
3. Inorganic Polymers: These include polymers containing no carbon
atoms. Their are composed of different atoms joined by chemical
bonds, while weaker intermolecular forces act between their chains.
Polysilanes, polygermanes, polysilicic acid, polyphosphates,
polyarsenates, etc., are examples of inorganic polymers.
Polymerization Processes
The processes of polymerization were classified by the W H Carothers (1926)
into two groups, i.e., condensation and addition polymerizations. In 1953, Flory
amended, Carother’s original distinction between addition and condensation
polymerization. He laid special emphasis on the mechanisms by which the two
types of polymerization, proceed. It was observed that condensation polymerization
was preceded by the stepwise intermolecular condensation of reactive groups
and the addition polymerization resulted from chain reactions involving some sort
of active centres. Thus, the two classes of polymerzation are:
Condensation Polymerization
This is entirely analogous to condensation in low molecular weight compounds.
For the formation of condensation polymer there is union between two
polyfunctional molecules to produce the large polyfunctional molecule. The process
involves the elimination of a small molecule, such as water, ammonia, etc. The
reaction continues until almost all of the reagents is used up. Since there is an
equilibrium between reactants and products, the rate of conversion can be controlled
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Material 161
Fundamentals of by the rate of removal of one of the products. A good example is, esterification,
Polymers
where water is eliminated between an acid and an alcohol.
NOTES
Here, the rate of conversion can be controlled by the rate of removal of

water.
Addition or Chain-Reaction Polymerization
This type of polymerization involves chain reactions. The chain carrier in such
reactions, may be an ion or a reactive substance with one unpaired electron called
a free radical. Chain polymerization is characteristic of compounds with multiple
bonds, for example, ethylene CH2=CH2. isobutylene (CH3)2 C=CH2 and vinyl
chloride CH2=CHCl, or of unstable rings containing heteroatoms, for example,
ethylene oxide . Depending upon the active centre, which may be a free
radical or an ion, the reaction is one of radical or ionic polymerization, respectively.
A free radical is produced by the decomposition of an initiator. The free radical
then attacks to open the double bond of a vinyl monomer or ring or a cyclic
compound and adds to it, with an electron remaining unpaired. Within a very short
span of time (usually a few seconds or less) may more monomers add successively
to form a long chain with active centers. Finally, chain termination results from
saturation of the macro radical and may occur by the combination of free radicals,
disproportionation of chain transfer.
With few exceptions, chain-reaction polymerization results in the formation
of homochain polymers, where as step-reaction polymerization produces
heterochain polymers. Polymerizations are classified without regard to loss of a
small molecule (for example, polyurethanes are formed by step-reaction
polymerization or type of interunit linkage (for example, phenol-formaldehyde resins
results from stepwise polymerization even though they lack interunit functional
groups). In case the differentiation is required on the basis of mechanism, the
terms step-reaction and chain-reaction are used; but to avoid confusion, the
common terms condensation and addition are permissible.
Check Your Progress

1. Define polymerization .
2. In how many classes polymerization distinguished ?
3. What is condensation polymerization ?
4. How is addition polymerization carried out?
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Fundamentals of
8.3 INITIATORS: TYPES AND INITIATOR Polymers
EFFICIENCY
Initiator, is a source of any chemical species that reacts with a monomer (single NOTES
molecule that can form chemical bonds) to form an intermediate compound that is
capable of linking successively with a large number of other monomers into a
polymeric compound.
The most commonly used initiators produce free radicals (reactive atoms
or groups of atoms that contain odd numbers of electrons); examples of initiators
include peroxides and aliphatic azo compounds used to polymerize vinyl chloride,
methyl methacrylate, and other monomers.
Acid-forming systems such as boron trifluoride with traces of water react
with a monomer to produce a positively charged (cationic) intermediate. Such
initiation is used in the conversion of isobutylene to butyl rubber.
Reaction of metallic sodium and biphenyl produces an anionic initiator that
causes formation of polymer chains with reactive sites at both ends; these may be
further treated with a different monomer to yield block copolymers.
Polypropylene and high-density polyethylene are prepared by use of
Ziegler catalysts, which are initiators composed of organometallic compounds and
metallic halides, such as triethylaluminum and titanium tetrachloride.
Initiation
Initiation is the first step of the polymerization process. During initiation, an active
center is created from which a polymer chain is generated. Not all monomers are
susceptible to all types of initiators. Radical initiation works best on the carbon–
carbon double bond of vinyl monomers and the carbon–oxygen double bond
in aldehydes and ketones. Initiation has two steps. In the first step, one or
two radicals are created from the initiating molecules. In the second step, radicals
are transferred from the initiator molecules to the monomer units present. Several
choices are available for these initiators.
Types of Initiation and the Initiators
Thermal Decomposition
The initiator is heated until a bond is homolytically cleaved, producing two radicals.
This method is used most often with organic peroxides or azo compounds
Thermal decomposition of dicumylperoxide

Photolysis
Radiation cleaves a bond homolytically, producing two radicals (Refer Figure 8.8).
This method is used most often with metal iodides, metal alkyls, and azo compounds Self-Instructional
Material 163
Fundamentals of
Polymers
Photolysis of azoisobutylnitrile (AIBN)

Photoinitiation can also occur by bi-molecular H abstraction when the radical is in
NOTES
its lowest triplet excited state.
An acceptable photoinitiator system should fulfill the following requirements:
 High absorptivity in the 300–400 nm range.
 Efficient generation of radicals capable of attacking the olefinic double bond
of vinyl monomers.
 Adequate solubility in the binder system (prepolymer + monomer).
 Should not impart yellowing or unpleasant odors to the cured material.
 The photoinitiator and any byproducts resulting from its use should be non-
toxic.
Redox Reactions
Reduction of hydrogen peroxide or an alkyl hydrogen peroxide by iron.Other
reductants such as Cr2+, V2+, Ti3+, CO2+, and Cu+ can be employed in place of
ferrous ion in many instances
Three steps involved in ionizing radiation: ejection, dissociation, and electron-

capture
Ionizing Radiation
α-, β-, γ-, or x-rays cause ejection of an electron from the initiating species,
followed by dissociation and electron capture to produce a radical.
(Top) Formation of radical anion at the cathode; (bottom) formation of

radical cation at the anode
Electrochemical
Electrolysis of a solution containing both monomer and electrolyte. A monomer
molecule will receive an electron at the cathode to become a radical anion, and a
monomer molecule will give up an electron at the anode to form a radical cation
(Refer Figure 8.11). The radical ions then initiate free radical (and/or ionic)
polymerization. This type of initiation of especially useful for coating metal surfaces
with polymer films
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164 Material
Fundamentals of
Polymers
NOTES
Plasma
A gaseous monomer is placed in an electric discharge at low pressures under
conditions where a plasma (ionized gaseous molecules) is created. In some cases,
the system is heated and/or placed in a radiofrequency field to assist in creating
the plasma.
Sonication
High-intensity ultrasound at frequencies beyond the range of human hearing
(16 kHz) can be applied to a monomer. Initiation results from the effects
of cavitation (the formation and collapse of cavities in the liquid). The collapse of
the cavities generates very high local temperatures and pressures. This results in
the formation of excited electronic states, which in turn lead to bond breakage and
radical formation.
Ternary Initiators
A ternary initiator is the combination of several types of initiators into one initiating
system. The types of initiators are chosen based on the properties they are known
to induce in the polymers they produce. For example, poly(methyl methacrylate)
has been synthesized by the ternary system benzoyl peroxide-3,6-bis (o-
carboxybenzoyl -N- isopropylcarbazole- di-η5- indenylzicronium dichloride (Refer
Figure 8.12).
Benzoyl peroxide-3,6-bis (o-carboxybenzoyl) -N-isopropylcarbazole- di-

ç5- indenylzicronium dichloride
This type of initiating system contains a metallocene, an initiator, and a
heteroaromatic diketo carboxylic acid. Metallocenes in combination with initiators
accelerate polymerization of poly(methyl methacrylate) and produce a polymer
with a narrower molecular weight distribution. The example shown here consists
of indenylzirconium (a metallocene) and benzoyl peroxide (an initiator). Also,
initiating systems containing heteroaromatic diketo carboxylic acids, such as 3,6-
bis (o-carboxybenzoyl) -N- isopropylcarbazole in this example, are known to
catalyze the decomposition of benzoyl peroxide. Initiating systems with this
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Material 165
Fundamentals of particular heteroaromatic diket carboxylic acid are also known to have effects on
Polymers
the microstructure of the polymer. The combination of all of these components—
a metallocene, an initiator, and a heteroaromatic diketo carboxylic acid—yields a
ternary initiating system that was shown to accelerate the polymerization and produce
NOTES polymers with enhanced heat resistance and regular microstructure.
Initiator Efficiency
Due to side reactions and inefficient synthesis of the radical species, chain initiation
is not 100%. The efficiency factor f is used to describe the effective radical
concentration. The maximal value of f is 1, but typical values range from 0.3 to
0.8. The following is a list of reactions that decrease the efficiency of the initiator.
Primary Recombination
Two radicals recombine before initiating a chain (Refer Figure 8.13). This occurs
within the solvent cage, meaning that no solvent has yet come between the new
radicals. Primary recombination of BPO; brackets indicate reaction happening
within the solvent cage is given below
Other Recombination Pathways

Two radical initiators recombine before initiating a chain, but not in the solvent
cage. Recombination of phenyl radicals from the initiation of BPO outside the
solvent cage is given below:
Side Reactions
One radical is produced instead of the three radicals that could be produced . The
reaction of polymer chain R with other species in reaction is given below:
Polymeric materials possess a very wide range of physical properties, they are
hard or soft or rubber-like, brittle or tough and malleable and non-malleable.
These properties depends on the molecular structure of the polymer. The physical
properties depend to a great extent on whether the polymer is (i) completely
amorphous or (ii) partly crystalline. In an amorphous polymer the molecular chains
are all tangled up in a disordered manner. The long chain polymers generally exist
in the amorphous state this is because the long chains mostly exist in the random
coiled configuration, the solid is thus clastic. However, due to the presence of
some crystallinity the polymeric material is stiffer. Depending on the temperature
of the amorphous polymer may be glassy or leathery.
Group OH Cl CN NO2 H NH2 CH3
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166 Material
Most polymers are in the glassy state which is like that of a supercooled Fundamentals of
Polymers
liquid. On raising the temperature there is a transition at the glass-transition
temperature from the glassy to the leathery state. Below the glass-transition
temperature of a polymeric substance can be raised by vulcanisation due to cross-
linkages. NOTES
The mechanical properties of polymers are profoundly dependent on the
stereo-regularity of their chains. Polymers of monomers like styrene have symmetric
carbon atoms. There are two types of stereoregular vinyl polymers, isotactic and
syndictactic depending on whether successive pseudoasymmetric carbon atoms
have the same or opposite enantiomorphic configuration. Some polymers contain
regions in which the chains are arranged in an orderly three dimensional array.
These crystalline regions typically have dimensions of the order of 10 mm and they
have an important influence on the physical properties of the polymer. The extent
of crystallinity of the polymer is increased as it is stretched. This because on
stretching the chains are drawn together thus reducing the random thermal motion.
Check Your Progress

5. What is a initiator ?
6. What does initiators produce ?
7. How does conversion of isobutylene to butyl rubber occur ?
8. How are block copolymers formed ?

QUESTIOS
1. Polymerization is the process in which relatively small molecules,
called monomers, combine chemically to produce a very large chain like or
network molecule, called a polymer.
2. The two classes of polymerization usually that are distinguished are as follows:
 Condensation Polymerization
 Addition Polymerization
3. In condensation polymerization, each step of the process is accompanied
by the formation of a molecule of some simple compound, often water.
In addition polymerization, monomers react to form a polymer without the
formation of by-products.
4. Addition polymerization is usually carried out in the presence of catalysts,
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Material 167
Fundamentals of 5. Initiator, is a source of any chemical species that reacts with
Polymers
a monomer (single molecule that can form chemical bonds) to form an
intermediate compound that is capable of linking successively with a large
number of other monomers into a polymeric compound.
NOTES 6. The most commonly used initiators produce free radicals (reactive atoms
or groups of atoms that contain odd numbers of electrons); examples of
initiators include peroxides and aliphatic azo compounds used to
polymerize vinyl chloride, methyl methacrylate, and other monomers.
7. Acid-forming systems such as boron trifluoride with traces of water react
with a monomer to produce a positively charged (cationic) intermediate.
Such initiation is used in the conversion of isobutylene to butyl rubber.
8. Reaction of metallic sodium and biphenyl produces an anionic initiator that
causes formation of polymer chains with reactive sites at both ends; these
may be further treated with a different monomer to yield block copolymers.
8.5 SUMMARY
 Polymerization, is a process in which relatively small molecules,

 The monomer molecules may be all alike, or they may represent two, three,
or more different compounds.
 In condensation polymerization, each step of the process is accompanied
by the formation of a molecule of some simple compound, often water.
In addition polymerization, monomers react to form a polymer without the
formation of by-products.
 Addition polymerization is usually carried out in the presence of catalysts,
 Linear polymers, are composed of chainlike molecules, may be
viscous liquids or solids with varying degrees of crystallinity; a number of
them can be dissolved in certain liquids, and they soften or melt upon heating.
 Cross-linked polymers, in which the molecular structure is a network, are
thermosetting resins (i.e., they form under the influence of heat but, once
formed, do not melt or soften upon reheating) that do not dissolve in solvents.
Both linear and cross-linked polymers can be made by either addition or
condensation polymerization.
 Polymers are very different from the other kinds of organic molecules that
you have seen so far. Whereas other compounds are of relatively low molar
mass, polymers are giant molecules of very high molar mass.
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 Polymers are the primary components of all sorts of plastics and related Fundamentals of
Polymers
compounds. A polymer is a large molecule formed of many smaller molecules
covalently bonded in a repeating pattern.
 An addition polymer is a polymer formed by chain addition reactions
NOTES
between monomers that contain a double bond. Molecules of ethene can
polymerize with each other under the right conditions to form the polymer
called polyethylene.
 Propagation is the new free radical compound interacts with another alkane,
continuing the process of chain growth.
 Termination occurs whenever two free radicals come in contact with one
another (not shown). The two free electrons form a covalent bond and the
free radical on each molecule no longer exists.
 Polyethylene can have different properties depending on the length of the
polymer chains and on how efficiently they pack together. Some common
products made from different forms of polyethylene include plastic bottles,
plastic bags, and harder plastic objects such as milk crates.
 Polyisoprene is a polymer of isoprene and is better known as rubber. It is
produced naturally by rubber trees, but several variants have been developed
which demonstrate improvements on the properties of natural rubber.
 Initiator, is a source of any chemical species that reacts with
a monomer (single molecule that can form chemical bonds) to form an
intermediate compound that is capable of linking successively with a large
number of other monomers into a polymeric compound.
 Acid-forming systems such as boron trifluoride with traces of water react
with a monomer to produce a positively charged (cationic) intermediate.
Such initiation is used in the conversion of isobutylene to butyl rubber.
 Reaction of metallic sodium and biphenyl produces an anionic initiator that
causes formation of polymer chains with reactive sites at both ends; these
may be further treated with a different monomer to yield block copolymers.
 Polypropylene and high-density polyethylene are prepared by use of
Ziegler catalysts, which are initiators composed of organometallic compounds
and metallic halides, such as triethylaluminum and titanium tetrachloride.
 Initiation is the first step of the polymerization process. During initiation, an
active center is created from which a polymer chain is generated. Not all
monomers are susceptible to all types of initiators. Radical initiation works
best on the carbon–carbon double bond of vinyl monomers and the carbon–
oxygen double bond in aldehydes and ketones.
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Material 169
Fundamentals of
Polymers 8.6 KEY WORDS
 Polymerization: Polymerization is a process of reacting monomer molecules

NOTES together in a chemical reaction to form polymer chains or three-dimensional
networks.
 Condensation polymerization: Condensation polymerization, each step
of the process is accompanied by the formation of a molecule of some
simple compound, often water. In addition polymerization, monomers react
to form a polymer without the formation of by-products.
 Addition polymerization: Addition polymerization usually are carried out
in the presence of catalysts, which in certain cases exert control over
structural details that have important effects on the properties of the polymer.
 Linear polymers: Linear polymers are composed of chain like molecules,
may be viscous liquids or solids with varying degrees of crystallinity; a number
of them can be dissolved in certain liquids, and they soften or melt upon
heating.
 Cross-linked polymers: Cross-linked polymers are the molecular structure
is a network, are thermosetting resins (i.e., they form under the influence
of heat but, once formed, do not melt or soften upon reheating) that do not
dissolve in solvents.
 Addition polymer: Addition polymer is a polymer formed by chain addition
reactions between monomers that contain a double bond.

EXERCISES

1. Define polymerization.
2. Brief a note on types of polymerization.
3. Brief a note on linear polymers.
4. What is addition polymers ?
5. Give polypropylene structure.
6. Give the structure of polyvinyl chloride
7. Brief a note on initiators.
1. Elaborate a not on polymerization and describe its types also.
2. Explain polyethylene synthesis.
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170 Material
3. Explain Initiation, propagation and termination. Fundamentals of
Polymers
4. Give a detailed note on initiators.
5. Give the polystyrene synthesis and its structure.
6. Explain types of initiation and the initiators. NOTES
7. Explain redox reactions and ionizing radiation
8. Discuss in detail about initiator efficiency.

& Company Ltd.
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Material 171
Stepwise Polymerization
UNIT 9 STEPWISE
POLYMERIZATION
NOTES
Structure
9.0 Introduction
9.1 Objectives
9.2 Stepwise Polymerization
9.3 Functionality of Monomers and Its Significance – Molar Masses
9.4 Degree of Polymerization
9.6 Summary
9.7 Key Words
9.0 INTRODUCTION
Step-growth polymerization refers to a type of polymerization mechanism in which
bi-functional or multifunctional monomers react to form first dimers, then trimers,
longer oligomers and eventually long chain polymers. Many naturally occurring and
some synthetic polymers are produced by step-growth polymerization, for example
polyesters, polyamides, polyurethanes, etc.
Due to the nature of the polymerization mechanism, a high extent of reaction
is required to achieve high molecular weight. IUPAC deprecates the term step-
growth polymerization and recommends use of the terms polyaddition, when the
propagation steps are addition reactions and no molecules are evolved during these
steps, and polycondensation when the propagation steps are condensation
reactions and molecules are evolved during these steps.
In this unit, you will study about stepwise polymerization, functionality of
monomers and its significance,molar masses and degree of polymerization in detail.
9.1 OBJECTIVES
after going through this unit, you will be able to:

 Understand what stepwise polymerization is
 Explain the functionality of monomers and its significance and molar masses
 Discuss degree of polymerization
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9.2 STEPWISE POLYMERIZATION
The reactions by which complex macromolecules are formed are not completely
understood. The process of building up polymers from simple repeating units NOTES
(monomers) can proceed with many variations. As noted earlier, on the basis of
mechanisms the two types of polymers are formed. Condensation polymers are
usually formed by the step-wise intermolecular condensation of the reactive groups,
addition polymers ordinarily result from chain reactions involving some sort of
active centres.
Most of the stepwise polymerizations are, stoichometrically, condensation
polymerization. A monomer can be converted into polymer by any reaction that
creates new bonds. Carother’s defined this number of new-bonds as the
functionality of a monomer in a given reaction. As the number of bonds formed
depends upon the number of reactive functional groups, the functionality of a
monomer can also be defined as the average number of reactive functional group
per molecule. In a condensation reaction, the type of the product formed is
determined by the functionality of the monomer. It should be obvious that a
monofunctional monomer gives only a low-molecular-weight product. A
functionality too can lead to linear structure. Polyfunctional monomer, with more
than two functional groups per molecule, give branched or cross-linked (three-
dimensional) polymers. The linear and the three-dimensional polymers differ widely
in their properties.
The most important reaction which has been used for the preparation of
condensation polymers is that addition and elimination at the carbonyl double
bond of carboxylic acids and their derivatives. The generalized reaction is
O
|
where R may be alkyl or aryl group, X may be OH, OR, NH2. NHR, O—
C—R, or Cl; and Y may be RO–, ROH, RNH2 or RCOO–. The metastable
intermediate can either return to the original state by Y or proceed to the final state
by eliminating X. The formation of polymers, polyamides, nylon—66 poly (ethylene
terephathalate), polyurethanes, polyureas, polysulphonamides, polyphenyl esters,
etc. provides some typical examples of this reaction.
In simple terms, it can be stated that stepwise polymerization is the
combination of several molecules by stepwise addition of the monomer molecules
to one another as a result of migration of some mobile atom, usually a hydrogen Self-Instructional
Material 173
Stepwise Polymerization atom, from one molecule to another. The formation of polyurethanes from di-
isocyanates and dihydric alcohols is illustrated below:
A trihydric alcohol will give a cross-linked polymer.
NOTES
Chain Polymerization
Chain polymerization is characteristic of unsaturated monomers. Ethenic
polymerization is an economically important class whose kinetics typify chain
polymerization. The terms ‘vinyl’, ‘olefin’ or ‘addition’ polymerization are often
used, although they are more restrictive. Flory showed conclusively that chain
polymerization proceeds by and requires the steps of interaction, propagation,
and termination typical of chain reactions in low-molecular-weight species. The
three stages which are essential to the formation of a high polymer can be
represented as:
1. Initiation: This involves the creation of an ‘active’ centre, and can also be
termed as activation of the monomer molecule, i.e.,
M  M*
(Excited monomer molecule or active centre)
2. Propagation: Propagation involves the addition of more monomer species
to the chain end. This occurs usually very rapidly (mol. wt. 107 in one-tenth
of a second) to final molecular weight value, as shown below.
M* + M  M*1
M*1 + M  M*2
M*2 + M  M*3
.....................
.....................
.....................
* *
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M n–1 + M Mn (Activated growing polymer molecule)
174 Material
3. Termination: In this step there is disappearance of the ‘active’ centre Stepwise Polymerization
M*n  Mn (Inactivated polymer molecule)

The active centre in chain polymerization reactions may be a free radical or
an ion, and the reaction is one of radical or ionic polymerization, respectively.
NOTES
Radical Polymerization
The intermediates having an odd number of electrons (an unpaired electron) are
known as free radicals. They can be generated in a number of ways, including
thermal decomposition of peroxides or hydroperoxides; photolytic decomposition
of covalently bonded compounds; dissociation of covalent bonds by high energy
radiation (-, -, -rays); oxidation reduction reactions; and electrochemical
interaction. However, the stability of the free radicals varies widely. Tertiary radicals
are more stable and less reactive than secondary radicals, which are in turn more
stable and less reactive than the primary ones. The benzyl radical is less reactive
than phenyl radical, the allyl is quite stable and is quite unreactive.
1. Initiation: Once the primary free radicals (free radicals produced in the
first stage) are produced by physical or chemical effects in the presence of
a vinyl monomer (CH2=CHX), the radical adds to the ethylenic double
bond of an unexcited monomer molecule with the regeneration of another
radical. If the radical formed by decomposition of initiator R–R is designated
R.
decomposition
R – R ¾¾¾¾¾¾ ® 2R (Primary free radical)
CH2=CHX + R. ¾¾¾¾® RCH2CH.— X (chain radical)

The regeneration of the new radical is characteristic of chain reactions
as this is capable of further interaction with the initial monomers. The efficiency
with which radicals initiate can be estimated by comparing the amount of
initiator decomposed with the number of polymer chains formed. Most
initiator in vinyl polymerisations have 60–100 per cent efficiency. The low
efficiency is mainly due to the recombination of the radical pairs before they
move apart, this is known as the cage-effect.
2. Propagation: The chain radical formed in the initiation step is capable of
adding successive monomers to from macroradicals. The chain propagation
reaction determines the rate of the polymerization, the molecular mass of
polymer, the structure of the polymer chain, i.e., the mode of monomer
addition (‘head-to-head’ or head-to-tail)*, the degree of branching, etc.
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Material 175
Stepwise Polymerization Addition according to the former scheme is called head-to-tail, configuration
in which the substituents occur on alternate carbon, atoms, and that according
to the latter scheme head-to-head or tail-to-tail In most polymerizations,
monomers combine according to most favoured (steric factors) head-to-
NOTES tail scheme.
The propagation step is given by following reaction:
R(CH2–CHX)n CH2–X + CH2–CHX
R(CH2–CHX)n+1 CH2 – CHX
Macro Radical
3. Termination: Propagation would continue until the supply of monomer is
exhausted. The radicals also have the strong tendency to react in pairs to
form a paired-electron convalent bond causing thereby loss of activity. In
fee radical polymerzation, this tendency is compensated by the small
concentration of radical species compared to monomers. Chain termination
results from saturation (deactivation) of the macroradical and may occur in
two ways:
(i) Combination or Coupling: Combination consists in the neutral saturation
of two macroradicals or of a macroradical and a low molecular weight free
radical:
(ii) Disproportionation: This involves the transfer of a hydrogen atom from

one macroradical to another to form two macromolecules with one saturated
and one unsaturated end group.
Chemical substances capable of reacting with free radicals to terminate the

reaction chain are called polymerization inhibitors, for example–
hydroquinone and trinitrobenzene. Chemical compounds which are only
chain transfer agents and do not affect the rate of polymerization but
determine the molecular mass of polymer are termed as polymerization
regulators or modifiers.
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176 Material
Ionic Polymerization Stepwise Polymerization
Chain reaction polymerization can occur by several mechanisms other than those
involving free radicals as discussed earlier. The most important among these are
the reactions in which the chain carriers are carbonium ions (cationic polymerization) NOTES
or carbanions (anionic polymerization). Ionic polymerization proceeds in the
presence of catalysts and is also called catalytic polymerisation. The reactivity of
the ethenic monomers to polymerization by radicals, ions and complexing agents
varies with the structure in a manner which can be correlated though not always
quantitatively predicated. It can be seen that, for the vinyl monomer (CH2=CH–
X), cationic initiation is favoured when X is electron releasing and anionic when X
is electron-withdrawing. This is because monomers with electron releasing groups
attached to the double-bonded carbons are capable of forming stable carbonium
ions, where as monomers with electron with-drawing substituents form stable
carbanions. Ionic polymerizations tend to be very rapid even at low temperatures.
The polymerization of isobutylene with AlCl3 or BF3 is carried out commercially
at —100ºC and an estimate of the life-time of a growing chain of isobutylene in
this case is about 10–6 sec, much shorter than the usual life time of a free-radical
chain.
1. Cationic or Carbonium Polymerization: This involves the formation
of a carbonium ion which is a polar compound with tricovalent carbon
atom carrying a positive charge, R–CH–R. Typical catalysts for cationic
polymerization are compounds with pronounced electron acceptor
properties (Lewis acids), for example, AlCl3, AlBr3, SnCl4, BF3,
H2SO4 and other strong acids. The cationic polymerization, involves
the carbonium ion as the chain carrier. Carbonium ion ineracts with a
monomer molecule, the reaction of chain growth being accompanied
with the communication of positive charge along the chain.
Consequently, the growing chain itself is a cation with a molecular
mass increasing in the course of polymerization. For example, the
polymerization of isobutylene in the presence of boron trifluoride
catalyst can be represented as:
BF3 + H2O  H+ (BF3OH)–
Catalyst-cocatalyst
complex
The catalyst-cocatalyst complex formed in step (I) donates a proton
to an isobutylene molecule to give carbonium ion.
H+ + (CH3)2 C = CH2 — (CH3)3C+
(from complex)
+ +
(CH3)3C + (CH3)2C = CH2—  (CH3)3 C — CH2 — C(CH3)2
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Material 177
Stepwise Polymerization +
(CH3)3 C — CH2 — C(CH3)2 + (CH3)2 C = CH2 – 
+
NOTES (CH3)3 C — CH2C (CH3)2 —CH2 — C (CH3)2
Thus, there is reformation of a carbonium ion at the end of each step
by the ‘head-to-tail’ addition of monomer to ion.
Chain termination apparently occurs as a result of the mutual collision
of the ends of growing ion to yield a polymer molecule with terminal
unsaturation and the original complex
+
(CH3)3 C — CH2 — C (CH3)2 — CH2 — C (CH3)2 + (BF3OH)–
+
(CH3)3 C — CH2 — C(CH3)2 — CH2 — C(CH3) = CH2 + H+ (BF3OH)–
Polymer
The third component present in low concentration which usually has
pronounced effects on polymerization is called cocatalyst. The efficiency
of the catalyst is dependent on the acid strength of the catalyst-
cocatalyst complex. In cationic polymerization, the catalyst is not in
the macromolecule.
2. Anionic or Carbanion Polymerization: Anionic polymerization
involves the formation of a carbanion, a compound with a trivalent
carbon atom carrying a negative charge. Catalyst for carbanion
polymerization include, alkali metals, alkali metal amides, alkoxides,
alkyls, aryls, hydroxides and cyanides. They are electron releasing
groups. Polymerization occur by the carbanion mechanism in the case
of monomers containing electronegative substituents at one of the
carbon atoms connected by a double bond. The initiation of ionic
chains involves the addition of a negative ion to the monomers, with
the opening of a ring or bond and growth at one end
The more basic the ion (anion), the better it serves to initiate chains.
–
Thus, C6H5 CH2- is powerful initiator than H2 which is stronger
–
than OH in the anionic polymerization of styrene.
The chain growth reaction is always accompanied with a transfer of a
negative charge along the chain, consequently, the growing chain is
always an anion of growing size.
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178 Material
Chain termination occurs as a result of the collision of a growing ion Stepwise Polymerization
with a molecule of the medium, such as an ammonia molecule:

– –
H2N(CH2– CH) CH2 – CHX + NH3 –H2N(CH2 – CH)n CH2 – CH2 X + NH2
| n | NOTES
X X
Thus, energy growing chain contains the –NH2 group. The termination
step is always unimolecular and usually be transfer.
It anionic polymerization, the end group of a growing molecule
possesses high activity and great stability. Hence, the polymers obtained
by anionic polymerization method retain active centres at the end of
the chain, which are capable of initiation the polymerization of
monomers. Such polymers are called living polymers. The polymer
can be ‘killed’ by addition of a terminating agent, like water at the end
of the reaction. Anionic polymerization has great advantages, since
spontaneous chain termination does not occur.
Check Your Progress

1. What is stepwise polymerization ?
2. How Condensation polymers are formed ?
3. How is a monomer converted into polymer?
4. Define the functionality of a monomer.
5. What is chain polymerization?
9.3 FUNCTIONALITY OF MONOMERS AND ITS

SIGNIFICANCE – MOLAR MASSES
Since polymerization reactions of both synthetic and natural, can lead to high
molecular weight compounds, the reaction chain is however broken by some
termination process that usually occurs in a random manner with respect to the
size, to which the polymer has already grown. It follows, therefore, that polymers
possess a range of molecular weights and that any data for the size or weight of
the molecules of polymer must represent some sort of average value. The molecular
weights of polymers lend themselves to two types of averages, i.e., (i) number
average molecular weights and (ii) weight average molecular weights.
Number average molecular weight: It is defined as the weight of the
sample divided by the total number of moles n in the sample, i.e.,
Weight
Mn =
n
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Material 179
Stepwise Polymerization If a method of molecular weight determination leads to the number of
particles, or molecules; that are present, in a given weight of a sample, it will give
the number average molecular weight. Let us consider a polymer as made up of
fractions consisting of n1 moles of molecular weight M1, n2 moles of molecular
NOTES weight M2 and so on, then Mn the number average molecular weight is given by
the expression:
n1 M1  n2 M 2  ....
Mn = ...(1)
n1  n2 ....
 n1 M i
i
Mn = ...(2)
 ni
i
On the other hand if in an experiment each particle makes a contribution to

the measured result according to its molecular weight, we get weight average
molecular weight of the polymer, Mw which is defined as,
 n1 Mi2
i
Mw = ...(3)
 ni M i
i
Molecular weight of a polymer can be determined by relative or absolute

methods. Many properties of polymers which depend upon molecular weight,
such as –solubility, elasticity, absorption on solids, and their tear strength, can be
corrected with an average molecular weight. Once correlated, the property can
be used as a measure of molecular weight. The weight determination can be done
by chemical or physical methods of functional group analysis, by measurement of
the colligative properties, light scattering or ultra-centrifugation or by measurement
of dilute solution viscosity. In all these methods, except the last, molecular weights
can be calculated without reference to calibration by another method and therefore,
are absolute methods. Dilute solution viscosity is not a direct measure of molecular
weight. All molecular weight methods, except a few end group analysis methods,
require solubility of the polymer and all involve extrapolation to infinite dilution of
operation in a solvent in which ideal solution behaviour is attained. Some important
methods used in practice for determining the molecular weight and size of
macromolecules in dilute solutions are discussed below.
Check Your Progress

6. How is molecular weight of a polymer determined ?
7. What is the procedure for weight determination?
8. How is number average molecular weight determined?
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180 Material
9.4 DEGREE OF POLYMERIZATION
Some of the important methods employed for the determination of molecular weights
of polymers are: NOTES
Osmometry
Osmometry can be used for determining molecular masses from 104 to 106. This
is one of the most accurate methods, though due to its lengthy and tedious
experimental procedure it cannot be frequently used for fast molecular weight
determination. The method, involves the measurement of the osmotic pressure of
solutions at several concentrations. The instrument used for the determination of
molecular-weights by this method is called osmometer. In an osmometer, the
solvent is separated from the solution by a semipermeable membrane. It then
passes through the latter into the solution, until the level of the solution in the
capillary stops rising. The osmotic pressure, at this stage, is equal to the weight of
the hydrostatic column of the solution.
McMillan and Mayer showed that the osmotic pressure of non-electrolytes
could be represented by a power series in the concentrations exactly like the virial
equation for a non-ideal gas,
 C 
 = RT   BC 2  DC 3  .... 
M
 n 
where C is the concentration in mass per unit volume. In a fairly dilute
solution of a polymer
 RT
=  RTBC
C Mn

In low concentrations region a plot of vs should give a straight line.
C
The capillary forces also raise the liquid in the capillary to some extent, to
account for these forces a capillary having radius equal to that of osmometer
capillary, is immersed in the liquid. This capillary is known as control capillary. The
difference in the level of osmometer capillary and control capillary is the measure
of osmotic pressure. The two more commonly used methods are:
1. Static Method: This method involves the measurement of the
equilibrium difference of levels in the osmometer. The osmometer for
this method are very simple in design, but equilibrium in such an
osmometer is reached after a long time. The concentration of the
solution near the membrane may increase as a result of absorption of
polymer, at equilibrium. The shortcoming can be eliminated by proper
production and storage of membranes. For cross linking polymers
this method is usually not recommended.
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Material 181
Stepwise Polymerization 2. Dynamic Method: This method consists of measuring the rate of
penetration of solvent through the membrane, depending upon the
pressure applied. The main advantage of this method is that the
measurements take very less time as compared to the static method.
NOTES
Choice of Membrane: A choice of suitable membrane plays an important role in
osmometric measurements. The membrane should be permeable to the solvent
and impermeable to the polymeric solute. It should satisfy the following two
conditions:
 The membrane should not swell to any great extent in the solvent.
 It should have sufficient fine pores to allow the solvent molecules to pass
through freely.
These days membranes are prepared from cellophane and specially treated
films of denitrated cellulose nitrate. The untreated cellophane membranes have
small pore radius and subsequently take long time to reach equilibrium. To increase
the pore size, the cellophane is treated with ammonia solution or other reagents.
For this reason only cellophane is generally used for measuring molecular weights
of very low-molecular weight polymers. Denitrated cellulose nitrate membrancs
give better and much more satisfactory results.
The polymer is first throughly freed from impurities by reprecipitation before
determining the molecular-weight. A stock solution, usually 1 per cent is prepared
from a purified polymer. From the stock solution, working solutions of various
concentrations, varying from 0.075 per cent to 0.5 per cent are prepared by
dilution. One fifth of the one per cent solution is left undiluted for exact determination
of its concentration. In order to measure the osmotic pressure, a polymer solution
and pure solvent are placed on the opposite sides of a semipermeable membrane.
The membrane is so selected as to permit only solvent and not the polymer particles.
To establish equilibrium, the pressure on the solution side must be greater. The
osmotic pressure, can be measured at several concentrations either by waiting for
equilibrium or by measuring and compensating for pressures automatically.
To calculate molecular weight of a polymer the osmotic pressure values
obtained for the different solutions are divided by the corresponding concentrations
and the resulting reduced osmotic pressures are plotted in /Cn versus C. The
straight line obtained in this way is extrapolated to zero concentration as shown in
figure 9.1. The resulting values A (intercept with the ordinate axis) is substituted in
the equation given below and molecular weight is calculated.
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182 Material
NOTES
Fig. 9.1 Variation of reduced osmotic pressure with concentration
   RT
  = ...(4)
C
 n Cn o M
RT
or M= ...(5)
  
  Cn0
 Cn 
where, = osmotic pressure (g/cm2)h
h = difference in liquid levels at equilibrium, cm
 = density of solvent, g/cm3
C = concentration, g/cm3
T = absolute temperature, K
M = molecular-weight, g/mole
R = gas constant, 8.48 × 104 g-cm/(mole) (K)
Viscometry
The first person to draw attention to the usefulness of solution viscosity as a measure
of polymer molecular weight was Staudinger, who established the following
relationship:
sp = KMC ...(6)
where, sp = specific viscosity of polymer solution
K = constant
M = molecular weight of a dissolved polymer
C = concentration of polymer in solution
However, the above relation suffers from two serious drawbacks, first, the
coefficient K does not give a constant value, but it depends on the molecular
weight of a polymer and secondly, the equation represents the concentration
dependence of specific viscosity incorrectly. According to the above equation, the
reduced viscosity (ratio of the specific viscosity to the concentration) hsp/C, is
independent of concentration.
sp/C = KM ...(7) Self-Instructional
Material 183
Stepwise Polymerization But experimental data show that the sp/Cvs. C dependence is represented
graphically by a straight line with a definite slope. Hence, it would be more accurate
to relate molecular weight of a polymer to intrinsic (viscosity value that is
independent of the solution concentration) and not to specific viscosity. Thus,
NOTES Staudinger’s equation can be modified by the following empirical relation,
[] = KMa ...(8)
where, [] = intrinsic viscosity of a solution, K and a are the constants
characerizing the given polymer-solvent system.
Intrinsic viscosity is determined from the relative viscosity of the dissolved
polymer solutions. Then the specific and reduced viscosities are calculated and a
plot of sp/Cvs. C is made. The extrapolation of this line to zero concentration,
gives the value of []. K and a are calculated by plotting log []vs. log M, which
represents a straight line having slope, a and intercept log K.
log [] = log K + a log M. ...(9)
Hence, K and a, can be determined graphically. Using the same solvent for
which K and a, are determined, the viscosities can be calculated.
Owing to the simplicity of the equipment used (viscometer), this method
can be very conveniently used in the laboratory.
Light Scattering
Light scattering accounts for many phenomena including the colours of the sky the
rainbow, and of most white materials. A media may be transparent or turbid. The
turbidity of a medium is due to scattering of light. The scattering of light occurs
whenever a beam of light encounters matter. Similarly, when a polymer is dissolved
in a solvent, the light scattered by the polymer far exceeds that scattered by the
solvent, and is an absolute measure of molecular weight.
Debye gave a solution for the factor of internal interference P() for the
scattering particles of different shape. The Debye relationship is:
H C 1
=  2 A2C ...(10)
K MP ( )
where H is a lumped constant including geometric factors and also the
change in refractive index with polymer concentration for the particular system
being investigated.  is the angle at which the intensity of light is measured and C is
the concentration. A2, second virial coefficient and P() (function of molecular
shape) are derived from data. The light intensity factor K is derived from the
galvanometer reading Ig. The geometry and the scattering by solvent Igs is
compensated by
( I g  I gs )sin 
K= ...(11)
1  cos 2 
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184 Material
since at  = 0, P () = 1, it is customary to extrapolate to v = 0 as well as C Stepwise Polymerization
H C 1
= 0. A plot of vs C constant  and vs. sin2 (/2) give intercept 1/
K MP ( )
M. In Zimm plot, both can be done simultaneously where a net work is obtained. NOTES
This method is more precise and makes it possible to calculate the values of
molecular masses of polymers without assumption of the shape of macromolecules
in a solution.
The presence of dust particles or gelled polymer particles cause a major
practical problem in light scattering. A small concentration of these, obscures the
scattering by ordinary polymer particles and result in M w = . The removal of
dust can be done by ultra centrifugation.
Check Your Progress

9. Where is osmometry used?
10. What is osmometer?
11. Define osmotic pressure.
12. What does static method involves?

QUESTIONS
1. Stepwise polymerization is the combination of several molecules by stepwise
addition of the monomer molecules to one another as a result of migration
of some mobile atom, usually a hydrogen atom, from one molecule to another.
2. Condensation polymers are usually formed by the step-wise intermolecular
condensation of the reactive groups, addition polymers ordinarily result from
chain reactions involving some sort of active centres
3. A monomer can be converted into polymer by any reaction that creates
new bonds. Carother’s defined this number of new-bonds as the functionality
of a monomer in a given reaction.
4. As the number of bonds formed depends upon the number of reactive
functional groups, the functionality of a monomer can also be defined as the
average number of reactive functional group per molecule. In a condensation
reaction, the type of the product formed is determined by the functionality
of the monomer.
5. Chain polymerization is characteristic of unsaturated monomers. Ethenic
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Material 185
Stepwise Polymerization polymerization. The terms ‘vinyl’, ‘olefin’ or ‘addition’ polymerization are
often used, although they are more restrictive.
6. Molecular weight of a polymer can be determined by relative or absolute
methods. Many properties of polymers which depend upon molecular
NOTES weight, such as –solubility, elasticity, absorption on solids, and their tear
strength, can be corrected with an average molecular weight.
7. The weight determination can be done by chemical or physical methods of
functional group analysis, by measurement of the colligative properties, light
scattering or ultra-centrifugation or by measurement of dilute solution
viscosity.
8. If a method of molecular weight determination leads to the number of
particles, or molecules; that are present, in a given weight of a sample, it will
give the number average molecular weight.
9. Osmometry can be used for determining molecular masses from 104 to
106. This is one of the most accurate methods, though due to its lengthy
and tedious experimental procedure it cannot be frequently used for fast
molecular weight determination.
10. The instrument used for the determination of molecular-weights by this
method is called osmometer.
11. The difference in the level of osmometer capillary and control capillary is
the measure of osmotic pressure.
12. Static method involves the measurement of the equilibrium difference of
levels in the osmometer.
9.6 SUMMARY
 The reactions by which complex macromolecules are formed are not

completely understood. The process of building up polymers from simple
repeating units (monomers) can proceed with many variations.
 Most of the stepwise polymerizations are, stoichometrically, condensation
polymerization. A monomer can be converted into polymer by any reaction
that creates new bonds. Carother’s defined this number of new-bonds as
the functionality of a monomer in a given reaction.
 A functionality too can lead to linear structure. Polyfunctional monomer,
with more than two functional groups per molecule, give branched or cross-
linked (three-dimensional) polymers. The linear and the three-dimensional
polymers differ widely in their properties.
 Stepwise polymerization is the combination of several molecules by stepwise
addition of the monomer molecules to one another as a result of migration
of some mobile atom, usually a hydrogen atom, from one molecule to another.
 Chain polymerization is characteristic of unsaturated monomers. Ethenic
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186 Material
polymerization. The terms ‘vinyl’, ‘olefin’ or ‘addition’ polymerization are Stepwise Polymerization
often used, although they are more restrictive.

 The active centre in chain polymerization reactions may be a free radical or
an ion, and the reaction is one of radical or ionic polymerization, respectively.
NOTES
 Tertiary radicals are more stable and less reactive than secondary radicals,
which are in turn more stable and less reactive than the primary ones. The
benzyl radical is less reactive than phenyl radical, the allyl is quite stable and
is quite unreactive.
 Chain reaction polymerization can occur by several mechanisms other than
those involving free radicals as discussed earlier. The most important among
these are the reactions in which the chain carriers are carbonium ions (cationic
polymerization) or carbanions (anionic polymerization). Ionic polymerization
proceeds in the presence of catalysts and is also called catalytic
polymerisation.
 The reactivity of the ethenic monomers to polymerization by radicals, ions
and complexing agents varies with the structure in a manner which can be
correlated though not always quantitatively predicated.
 The polymerization of isobutylene with AlCl3 or BF3 is carried out
commercially at —100ºC and an estimate of the life-time of a growing
chain of isobutylene in this case is about 10–6 sec, much shorter than the
usual life time of a free-radical chain.
 Cationic or carbonium polymerization involves the formation of a carbonium
ion which is a polar compound with tricovalent carbon atom carrying a
positive charge, R–CH–R.
 The cationic polymerization, involves the carbonium ion as the chain carrier.
Carbonium ion ineracts with a monomer molecule, the reaction of chain
growth being accompanied with the communication of positive charge along
the chain.
 Anionic or carbanion polymerization involves the formation of a carbanion,
a compound with a trivalent carbon atom carrying a negative charge. Catalyst
for carbanion polymerization include, alkali metals, alkali metal amides,
alkoxides, alkyls, aryls, hydroxides and cyanides. They are electron releasing
groups.
 Polymerization occur by the carbanion mechanism in the case of monomers
containing electronegative substituents at one of the carbon atoms connected
by a double bond.
 The weight determination can be done by chemical or physical methods of
functional group analysis, by measurement of the colligative properties, light
scattering or ultra-centrifugation or by measurement of dilute solution
viscosity.
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Material 187
Stepwise Polymerization  Osmometry can be used for determining molecular masses from 104 to
106. This is one of the most accurate methods, though due to its lengthy
and tedious experimental procedure it cannot be frequently used for fast
molecular weight determination. The method, involves the measurement of
NOTES the osmotic pressure of solutions at several concentrations.
 Static method involves the measurement of the equilibrium difference of
levels in the osmometer. The osmometer for this method are very simple in
design, but equilibrium in such an osmometer is reached after a long time.
 The concentration of the solution near the membrane may increase as a
result of absorption of polymer, at equilibrium. The shortcoming can be
eliminated by proper production and storage of membranes.
 Dynamic method consists of measuring the rate of penetration of solvent
through the membrane, depending upon the pressure applied. The main
advantage of this method is that the measurements take very less time as
compared to the static method.
9.7 KEY WORDS
 Stepwise polymerization: Stepwise polymerization is the combination of

several molecules by stepwise addition of the monomer molecules to one
another as a result of migration of some mobile atom, usually a hydrogen
atom, from one molecule to another.
 Chain polymerization: Chain polymerization is characteristic of unsaturated
monomers. Ethenic polymerization is an economically important class whose
kinetics typify chain polymerization. The terms ‘vinyl’, ‘olefin’ or ‘addition’
polymerization are often used, although they are more restrictive.
 Osmometer: The instrument used for the determination of molecular-weights
by this method is called osmometer.
 Osmotic pressure: The difference in the level of osmometer capillary and
control capillary is the measure of osmotic pressure.

EXERCISES

1. What is stepwise polymerization?
2. What is chain polymerization ?
3. Write about the three steps involved in chain polymerization.
4. Brief a note on ionic polymerization.
Self-Instructional 5. Give short note on anionic polymerization.
188 Material
Long Answer Questions Stepwise Polymerization
1. Write a elaborated note on stepwise polymerization.

2. Explain chain polymerization and its three stages.
3. Write a detailed note on radical polymerization and its three stages. NOTES
4. Discuss in detail about ionic polymerization.
5. Give a detailed account on functionality of monomers and its significance
and molar masses.
6. Elaborate on degree of polymerization

& Company Ltd.
Self-Instructional
Material 189
Kinetics and Mechanism
Polymerization
UNIT 10 KINETICS AND
MECHANISM
NOTES
POLYMERIZATION
Structure
10.0 Introduction
10.1 Objectives
10.2 Kinetics and Mechanism of Free Radical
10.3 Cationic and Anionic Polymerization
10.5 Summary
10.6 Key Words
10.0 INTRODUCTION
In polymer chemistry, polymerization is a process of reacting monomer
molecules together in a chemical reaction to form polymer chains or three-
dimensional networks. There are many forms of polymerization and different
systems exist to categorize them. In chemical compounds, polymerization occurs
via a variety of reaction mechanisms that vary in complexity due to functional
groups present in reacting compounds and their inherent steric effects.
Alkenes form polymers through relatively simple radical reactions; in contrast, more
complex reactions such as those that involve substitution at the carbonyl
group require more complex synthesis due to the way in which reacting molecules
polymerize.
As alkenes can be formed in somewhat straightforward reaction
mechanisms, they form useful compounds such as polyethylene and Polyvinyl
Chloride (PVC) when undergoing radical reactions, which are produced in high
tonnages each year due to their usefulness in manufacturing processes of commercial
products, such as piping, insulation and packaging.
In this unit, you will study about the kinetics and mechanism of free radicals
And cationic and anionic polymerization in detail.
10.1 OBJECTIVES
 Understand the kinetics and mechanism of free radicals
 Explain cationic and anionic polymerization
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190 Material
10.2 KINETICS AND MECHANISM OF FREE Polymerization
RADICAL
Radical, also called Free Radical, in chemistry, molecule that contains at least one NOTES
unpaired electron. Most molecules contain even numbers of electrons, and the
covalent chemical bonds holding the atoms together within a molecule normally
consist of pairs of electrons jointly shared by the atoms linked by the bond. Most
radicals may be considered to have arisen by cleavage of normal electron-pair
bonds, every cleavage having produced two separate entities, each of which
contains a single, unpaired electron from the broken bond (in addition to all the
rest of the normal, paired electrons of the atoms).
Although free radicals contain unpaired electrons, they may be electrically
neutral. Because of their odd electrons, free radicals are usually highly reactive.
They combine with one another, or with single atoms that also carry free electrons,
to give ordinary molecules, all of whose electrons are paired; or they react with
intact molecules, abstracting parts of the molecules to complete their own electron
pairs and generating new free radicals in the process. In all these reactions, each
simple free radical, because of its single unpaired electron, is able to combine with
one other radical or atom containing a single unpaired electron. Under special
circumstances, diradicals can be formed with unpaired electrons on each of two
atoms (giving an overall even number of electrons), and these diradicals have a
combining power of two.
Certain free radicals are stabilized by their peculiar structures; they exist for
appreciable lengths of time, given the right conditions. Most free radicals, however,
including such simple ones as the methyl (·CH3) and ethyl (·C2H5) radicals, are
capable of only the most fleeting independent existence.
Stable Radicals
The first relatively stable free radical, triphenylmethyl (structure I), was discovered
by Moses Gomberg in 1900. In this compound the central carbon is trivalent since
it is combined with three substituents instead of four, and its unshared electron is
represented by a dot. Free radicals of the triphenylmethyl type are stable only in
certain organic solvents; they are rapidly destroyed by irreversible reactions in the
presence of air, water, or strong acids.
In a manner analogous to the above, free radicals are formed by the breaking of
the nitrogen–nitrogen bond in aromatic hydrazines of the general structure
R2N―NR2, or of the central nitrogen–nitrogen bond in aromatic tetrazanes,
R2N―RN―NR―NR2. Thus, the radical 1,1-diphenyl-2-picrylhydrazyl (structure
II) exists as a stable violet solid.
Similar examples of free radicals, in which, however, the odd electron is on oxygen,
are also known, for example, the 2,4,6-tri-tert-butylphenoxy radical (structure
III).
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Material 191
Polymerization
NOTES
Still another type of stable radical ion, a metal ketyl, forms when a substance
such as benzophenone, is treated with metallic sodium to give the coloured
substance (C6H5)2C―O-. Similarly, sodium reacts with complex aromatic
hydrocarbons such as naphthalene, converting them to highly coloured radical
ions.
A final class of relatively stable organic free radicals are those containing the
group > NO. An example is diphenylnitrogen oxide, (C6H5)2NO, which is obtained
by the oxidation of diphenylhydroxylamine, (C6H5)2NOH.
Certain structural features appear to be required for the existence of stable

free radicals. One condition of particular importance is shown by the semiquinone
radical ion IV. As depicted, the upper oxygen atom has a negative charge and the
lower one an odd electron. This assignment is arbitrary, however, and the same
molecule would be represented if the charge and the odd electron were
interchanged. When such a situation is encountered, the actual average distribution
of electrons within the molecule is presumed not to be that of either of the structures
just described but to be intermediate between the two. This circumstance is called
delocalization, or resonance; according to quantum mechanics,
the resonance considerably increases the stability of the substance and, as in this
case, the probability of its existence. Similar arguments account for the stability of
the other free radicals discussed earlier.
Unstable Radicals
Simple free radicals such as methyl, ·CH3, also exist and play key roles as transient
intermediates in many chemical reactions. The existence of the methyl radical was
first demonstrated by Friedrich A. Paneth and W. Hofeditz in 1929 by the following
experiment. The vapours of tetramethyllead, Pb(CH3)4, mixed with gaseous
Self-Instructional
192 Material
hydrogen, H2, were passed through a silica tube at low pressure. When a portion Kinetics and Mechanism
Polymerization
of the tube was heated to about 800° C, the tetramethyllead was decomposed
and a mirror of metallic lead deposited on the internal surface of the tube. The
gaseous products of the decomposition were found capable of causing the
disappearance of a second lead mirror, deposited at a more distant cool point in NOTES
the tube.
Since none of the recognized stable products of the decomposition was
able similarly to dissolve a lead mirror, the inference was drawn that methyl radicals
formed in the high-temperature decomposition reacted with lead at the cool mirror
to regenerate tetramethyllead.
Methyl radicals obtained in this way proved to be highly reactive and short-
lived. They not only reacted with lead and other metals but also disappeared
rapidly and spontaneously, largely by dimerization to ethane, H3C―CH3.
Techniques for producing reactive free radicals in the gas phase have been greatly
extended by subsequent research. It has been found that various unstable species,
such as ethyl, (·C2H5), propyl, (·C3H7), and hydroxyl, (·OH), can be obtained by
several methods including: (1) photochemical decomposition of a variety of organic
and inorganic materials, (2) reaction between sodium vapour and an alkyl halide,
and (3) discharge of electricity through a gas at low pressure. Atoms that arise
from dissociation of a diatomic molecule (for example, the chlorine atom, ·Cl,
from the dissociation of the chlorine molecule, Cl2) can also be obtained and have
the properties of short-lived radicals of this type.
The existence of the various known unstable free radicals is most commonly
demonstrated by the reactions that they undergo. Thus, ethyl radicals, formed
from tetraethyllead, Pb(C2H5)4, dissolve zinc and antimony mirrors. The resulting
ethyl derivatives of zinc and antimony, Zn(C2H5)2 and Sb(C2H5)3, have been
isolated and chemically identified. In a few instances, unstable radicals also have
been identified spectroscopically. Here the important technique of flash photolysis,
the use of a single, intense flash of light to produce a momentary high concentration
of free radicals, is used.
Transient, unstable free radicals also may be produced in solution by several
means. A number of molecules, of which organic peroxides are typical, possess
such weak chemical bonds that they decompose irreversibly into free radicals on
warming in solution. Diacetyl peroxide, for example, is considered to decompose,
at least in large part, into carbon dioxide, CO2, and methyl radicals. These, in turn,
rapidly attack most organic solvents, often by abstracting hydrogen to given
methane, CH4, together with other products. Irradiation of solutions of many organic
substances with ultraviolet light leads to the absorption of sufficient energy to disrupt
chemical bonds and produce free radicals, and, in fact, most photochemical
processes are at present thought to involve free-radical intermediates. The chemical
changes that occur when solutions (and also gases) are exposed to high-energy
radiation also appear to involve the transient formation of free radicals.
Self-Instructional
Material 193
Polymerization
It is generally considered that free radicals are transient intermediates in

NOTES
many high-temperature reactions (such as combustion and the thermal cracking
of hydrocarbons), in many photochemical processes, and in a number of other
important reactions in organic chemistry, although the concentrations of the free
radical intermediates are in general too low for direct detection. One class of free-
radical reaction is of particular importance and is illustrated by the following example.
Methane, CH4, reacts with chlorine, Cl2, by an overall process that gives
chloromethane, CH3Cl, and hydrogen chloride, HCl. The reaction is enormously
accelerated by light and apparently involves the following steps:
1, 2, 3, 4
Chlorine atoms are produced in (1) and destroyed in (4), while the products that
are actually isolated arise from (2) and (3). Since chlorine atoms consumed in (2)
are regenerated in (3), a single atom of chlorine can lead to the production of
many molecules of chloromethane. Such processes, in which an intermediate is
continually regenerated, are known as chain reactions, and their study constitutes an
important branch of chemical kinetics. Similar chains involving transient free radicals
are involved in the halogenation of many other organic molecules, in many of
the polymerization reactions that are employed in the manufacture of plastics
and synthetic rubber, and in the reaction of molecular oxygen, O2, with a great
number of organic molecules.
Magnetic Properties of Free Radicals
The magnetic properties of free radicals provide a powerful tool for their detection
and study. Molecules with even numbers of paired electrons are diamagnetic,
.i.e., they are slightly repelled by a magnet. Free radicals, however, are paramagnetic
(attracted by a magnet) because of the spin of the odd electron, the spins of the
remaining paired electrons effectively canceling each other. The magnetic property
of a substance most commonly studied is its magnetic susceptibility, effectively its
behaviour in an inhomogeneous magnetic field, and the extent of paramagnetism of
the substance is described in terms of its magnetic dipole moment. The magnitude
of this dipole moment, which is the same for all free radicals containing single
electrons, can be calculated, and the value obtained (1.73 Bohr magnetons) has
been confirmed experimentally with free radicals in the solid state or at known
concentrations in solution. Magnetic susceptibility measurements may be used to
demonstrate the existence of free radicals and to measure the position
of equilibrium between radicals and their dimers or disproportionation products.
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194 Material
Diradicals, with even numbers of electrons, two of which, however, are not paired, Kinetics and Mechanism
Polymerization
are also paramagnetic, the oxygen molecule, O2, being probably the simplest
example of the kind.
The electron paramagnetic-resonance spectra of free radicals provide another
technique for their detection and study. According to quantum mechanics, the spin NOTES
of the odd electron of a free radical, when placed in a magnetic field, may have
two, and only two, orientations, one with and the other against the field. These
two orientations differ slightly in energy by an amount proportional to the strength
of the magnetic field, and the majority of the electrons have the orientation of
lower energy. If a system containing free radicals is placed in a magnetic field and
exposed to electromagnetic radiation (for example, in the region of very short
radio waves), molecules with the lower energy orientation absorb radiation of a
frequency corresponding to an energy just sufficient to flip the odd electron into its
higher energy state. This phenomenon gives rise in the simplest case to a
paramagnetic-resonance absorption spectrum consisting of a single sharp
absorption line.
The technique is sensitive and will detect extremely small concentrations of
free radicals, as little as one part in 107 having been reported detected. In many
organic free radicals, interaction of the odd electron with the magnetic moments of
the nuclei of different atoms in the molecule (most commonly with hydrogen nuclei)
gives rise to a more complicated system of energy levels and an absorption spectrum
consisting of a series of lines. The nature of the spectrum permits the identification
of particular free radicals and also gives information about their electronic structure.
Mechanism of Free Radical Polymerization
Free radical polymerization consists of three fundamental steps, initiation,
propagation, and termination. Initiation, involves the formation of radicals followed
by the radical’s reaction with a vinyl monomer, propagation is the rapid and
progressive addition of monomers to the growing polymer chain without a change
of the active center, and termination is the destruction of the growth active center,
usually by combination or coupling of the radicals of two growing polymer chains
or by disproportionation. In addition to these three processes, chain transfer might
occur, which is the transfer of the growth active site from the active chain to a
inactive (dormant) one, a monomer or a solvent molecule (transfer agent).
Initiation
This step involves the generation of active species. The free radicals can be
produced in a number of ways, including thermal or photochemical decomposition
of organic peroxides, hydroperoxides, azo or diazo compounds. Other methods
of free radical generation are high-energy radiation and oxidation-reduction (redox)
reactions.
Self-Instructional
Material 195
Kinetics and Mechanism The two most common initiators (I) are benzoyl peroxide (BPO) and 2,2'-
Polymerization
azo-bis- isobutyrylnitrile (AIBN). Both molecules have a strong tendency to fall
apart into two fragments with unpaired electrons, the so-called free radical initiators:
I → 2 R·
NOTES Following its generation, the free radical then reacts with a vinyl monomer,
that is, it adds to one of the electrons of the double bond of the vinyl monomer and
the remaining electron becomes the new free radical:
R· + M → RM·
Thus the process of chain initiation involves two steps; the first being the
decomposition of the initiator (for example, BPO or AIBN) to yield a pair of free
radicals R·, and the second the addition of a monomer to the primary radical R· to
yield the chain radical, which is called the initiation. It was found that the rate-
limiting step is the initiation step, that is, the rate constant for initiator dissociation is
much smaller than that for monomer addition.
Some of the monomers may also undergo other reactions such as combination
with another radical to form inactive molecules.
The efficiency of the radicals with which they initiate chains can be estimated
by comparing the number of initiators decomposed with the number of polymer
chains formed, that is, only a fraction f of the initiator concentration does initiate a
polymerization process. Based on observations, the rate of initiation is proportional
to the concentration of initiators [I] and the efficiency f:
Ri = d[M·] / dt = 2 f kd [I]
where kd is the rate constant (velocity coefficient) of initiation.
Propagation
The growth of a polymer chain by successive addition of monomers during
propagation can be represented as follows:
RM1· + M → RM2·
RM2· + M → RM3·
And in general:
RMx· + M  RMx+1·
The general assumption is that the radical reactivity is independent of the chain
length, this means, that all the propagation steps have the same rate
constant kp1 = kp2 = ... = kp. Thus, the rate of polymerization equals the
consumption of monomers in the propagation step. Since both a monomer and the
growing polymer chain are involved in the reaction, the reaction rate is proportional
to both concentrations.
Rp = -d[M] / dt = kp [M] [M*]
where kp is the reaction constant or velocity coefficient of the process and
[M*] = ∑RMx,
which is the sum of the concentration of all chain radicals.
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Termination Kinetics and Mechanism
Polymerization
The propagation step would theoretically continue until all monomers are consumed.
However, pairs of radicals also have a tendency to react with each other and thus
annihilate their activities. The termination can occur via combination or
NOTES
disproportionation. In the case of combination or coupling, two growing polymer
chains react with each other forming a single nonreactive polymer chain:
Mx· + My· → Mx+y
And in the case of disproportionation, a hydrogen atom is transferred from
one radical to the other resulting in two polymers, one with a saturated end and
the other with an unsaturated end and each with an initiator fragment.
Mx· + My· → Mx + M y
Usually, there is no need to distinguish between these two different types of
termination reactions, that is, both reactions can be combined to one rate
expression:
Rt = -d[M·] / dt = 2 kt [M·]2
Where the factor two occurs as a result of the disappearance of two radicals
at each incidence of termination reaction.
The rate of radical polymerization reaction usually increases with rising temperature.
The variation in temperature also effects the structure of the resulting products. To
illustrate— the rise in temperature during the polymerization of butadiene causes
ring dimer to form instead of chain molecules. That is why butadiene is always
polymerized below 60ºC. The size and structure of the polymer chain depends
upon the temperature. It has been established that low temperature favours formation
of higher molecular mass polymer in most of the cases.
Raising the temperature increases the degree of branching of a polymer.
Effect of Pressure
Pressure changes also have a marked effect on the rate of a polymerization. If
pressure is increased this would result in increase in the number of collisions between
the active centres and the monomers. Hence, the rate of polymerization will
considerably be increased. Further, the increase in pressure enable a lower
temperature of polymerization and hence the production of polymers with higher
molecular masses. For example, butadiene polymerization takes 45 hours at 7000
atm and 48ºC, and only 19 hours at the same pressure and 61ºC, but at 1 atm it
takes hundred of days.
Effect of Catalyst
Catalyst plays a vital role in the chain polymerization. Ionic polymerizations always
require a catalyst. In the presence of catalyst, the polymerization can be affected
at low pressure. The use of elevated pressure for polymerization should always be
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Material 197
Kinetics and Mechanism considered in conjunction with the choice of a catalyst. To illustrate polyethylene,
Polymerization
which could be produced formerly only at a pressure of 1000–2000 atm (high
pressure polyethene), can now be obtained by the Ziegler method involving the
use of triethyl aluminium and titanium chlorides as catalysts at a low pressure (low-
NOTES pressure polyethene).
Check Your Progress

1. What are radicals?
2. Brief about stable radicals.
3. What are unstable radicals?
4. How is thee existence of various unstable free radicals known ?
5. How does chemical changes occur when solutions are exposed to high-
energy radiation?
10.3 CATIONIC AND ANIONIC POLYMERIZATION
Butene undergoes polymerization under the influence of various reagents but the
product is not very satisfactory as a rubber substitute. Styrene is an aromatic
compound which on polymerisation gives polystyrene. Ordinary glass has the
weakness of being brittle. The development of clear transparent high polymers is
certainly one of the may achievements in polymer chemistry. Methyl methacrylate
readily polymerises yielding a clear transparent glass. This polymer, which is sold
under trade names such as plexiglas and lucite may be made into sheets or various
articles as desired. The injection molding process by which the polymer is forced
under pressure into a mold is widely used with this polymer. Methyl methacrylate
is used for transparent parts of airplanes.
Terephthalic acid combines with ethylene glycol which on condensation forms
a polymer molecule known as dacron.
The reactions can be symbolized as under:
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Polymerization
NOTES
The polymer is called polyethylene terephthalate and is sold by the trade

name of dacron.
Nylon can be prepared by condensing hexamethylene diamine with adipic
acid.
Organisilicon Polymers: Silicon is directly below carbon in the periodic table,

but the chief interest in silicon has been with respect to natural silicates in silica and
in glasses. The fact that silicon forms hydrides of the type Sin H2n+2. Silicon consists
of very large groups silicon atoms joined together through an oxygen atom. The
linkage –Si–O–Si–O–Si– seems to be very stable compounds in which the silicon-
oxygen bond occurs and in which the remaining valences are filled by hydrogens
are called siloxanes.
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Material 199
Kinetics and Mechanism Such molecules are quite large with many silicon atoms. These compounds
Polymerization
are called polysiloxanes.
NOTES
The recurring unit in polysiloxane is when the hydrogen
atoms are replaced by alkyl groups a typical organosilicon polymer is obtained.

Different organosilicon polymers are possible depending upon the choice of alkyl
or aryl groups and on the extent of cross-linking between the chains.
Most of the organosilicon polymers are oils and remain liquid at very low
temperatures and there is very small variation in viscosities with temperature and
are used as lubricants. Those silicones with extensive cross linking are solids. One
of the most important applications of organosilicones is as electrical insulating paste
for use as spark plug terminals for aircraft. The silicones do not burn and can stand
unusually high temperatures. Some organosilicones are used for making surfaces
water repellant.
Ionic Polymerization
Chain reaction polymerization can occur by several mechanisms other than those
involving free radicals as discussed earlier. The most important among these are
the reactions in which the chain carriers are carbonium ions (cationic polymerization)
or carbanions (anionic polymerization). Ionic polymerization proceeds in the
presence of catalysts and is also called catalytic polymerisation. The reactivity of
the ethenic monomers to polymerization by radicals, ions and complexing agents
varies with the structure in a manner which can be correlated though not always
quantitatively predicated. It can be seen that, for the vinyl monomer (CH2=CH–
X), cationic initiation is favoured when X is electron releasing and anionic when X
is electron-withdrawing. This is because monomers with electron releasing groups
attached to the double-bonded carbons are capable of forming stable carbonium
ions, where as monomers with electron with-drawing substituents form stable
carbanions. Ionic polymerizations tend to be very rapid even at low temperatures.
The polymerization of isobutylene with AlCl3 or BF3 is carried out commercially
at —100ºC and an estimate of the life-time of a growing chain of isobutylene in
this case is about 10–6 sec, much shorter than the usual life time of a free-radical
chain.
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1. Cationic or Carbonium Polymerization: This involves the formation Kinetics and Mechanism
Polymerization
of a carbonium ion which is a polar compound with tricovalent carbon
atom carrying a positive charge, R–CH–R. Typical catalysts for cationic
polymerization are compounds with pronounced electron acceptor
properties (Lewis acids), for example, AlCl3, AlBr3, SnCl4, BF3, NOTES
H2SO4 and other strong acids. The cationic polymerization, involves
the carbonium ion as the chain carrier. Carbonium ion ineracts with a
monomer molecule, the reaction of chain growth being accompanied
with the communication of positive charge along the chain.
Consequently, the growing chain itself is a cation with a molecular
mass increasing in the course of polymerization. For example, the
polymerization of isobutylene in the presence of boron trifluoride
catalyst can be represented as:
BF3 + H2O  H+ (BF3OH)–
Catalyst-cocatalyst
complex
The catalyst-cocatalyst complex formed in step (I) donates a proton
to an isobutylene molecule to give carbonium ion.
H+ + (CH3)2 C = CH2 — (CH3)3C+
(from complex)
+ +
(CH3)3C + (CH3)2C = CH2—  (CH3)3 C — CH2 — C(CH3)2
+
(CH3)3 C — CH2 — C(CH3)2 + (CH3)2 C = CH2 – 
+
(CH3)3 C — CH2C (CH3)2 —CH2 — C (CH3)2
Thus, there is reformation of a carbonium ion at the end of each step
by the ‘head-to-tail’ addition of monomer to ion.
Chain termination apparently occurs as a result of the mutual collision
of the ends of growing ion to yield a polymer molecule with terminal
unsaturation and the original complex
+
(CH3)3 C — CH2 — C (CH3)2 — CH2 — C (CH3)2 + (BF3OH)–
+
(CH3)3 C — CH2 — C(CH3)2 — CH2 — C(CH3) = CH2 + H+ (BF3OH)–
Polymer
The third component present in low concentration which usually has
pronounced effects on polymerization is called cocatalyst. The
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Material 201
Kinetics and Mechanism efficiency of the catalyst is dependent on the acid strength of the
Polymerization
catalyst-cocatalyst complex. In cationic polymerization, the catalyst is
not in the macromolecule.
2. Anionic or Carbanion Polymerization: Anionic polymerization
NOTES
involves the formation of a carbanion, a compound with a trivalent
carbon atom carrying a negative charge. Catalyst for carbanion
polymerization include, alkali metals, alkali metal amides, alkoxides,
alkyls, aryls, hydroxides and cyanides. They are electron releasing
groups. Polymerization occur by the carbanion mechanism in the case
of monomers containing electronegative substituents at one of the
carbon atoms connected by a double bond. The initiation of ionic
chains involves the addition of a negative ion to the monomers, with
the opening of a ring or bond and growth at one end
The more basic the ion (anion), the better it serves to initiate chains.
–
Thus, C6H5 CH2- is powerful initiator than H2 which is stronger
–
than OH in the anionic polymerization of styrene.
The chain growth reaction is always accompanied with a transfer of a
negative charge along the chain, consequently, the growing chain is
always an anion of growing size.
Chain termination occurs as a result of the collision of a growing ion
with a molecule of the medium, such as an ammonia molecule:
– –
H2N(CH2– CH) CH2 – CHX + NH3 –H2N(CH2 – CH)n CH2 – CH2 X + NH2
| n |
X X
Thus, energy growing chain contains the –NH2 group. The termination
step is always unimolecular and usually be transfer.
It anionic polymerization, the end group of a growing molecule
possesses high activity and great stability. Hence, the polymers obtained
by anionic polymerization method retain active centres at the end of
the chain, which are capable of initiation the polymerization of
monomers. Such polymers are called living polymers. The polymer
can be ‘killed’ by addition of a terminating agent, like water at the end
of the reaction. Anionic polymerization has great advantages, since
spontaneous chain termination does not occur.
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Polymerization
Check Your Progress
6. Define dacron.
7. What is styrene ? NOTES
8. What does silicon consists of ?
9. What does cationic or carbonium polymerization involves ?
10. What does catalyst for carbanion polymerization have ?

QUESTIONS
1. Radical, also called Free Radical, in chemistry, molecule contains at least
one unpaired electron. Most molecules contain even numbers of electrons,
and the covalent chemical bonds holding the atoms together within a molecule
normally consist of pairs of electrons jointly shared by the atoms linked by
the bond.
2. Stable Radicals is the first relatively stable free radical, triphenylmethyl
(structure I), was discovered by Moses Gomberg in 1900. In
this compound the central carbon is trivalent since it is combined with three
substituents instead of four, and its unshared electron is represented by a
dot.
3. Unstable Radicals are simple free radicals such as methyl, ·CH3, also exist
and play key roles as transient intermediates in many chemical reactions.
The existence of the methyl radical was first demonstrated by Friedrich
A. Paneth and W. Hofeditz in 1929 by the following experiment.
4. The existence of the various known unstable free radicals is most commonly
from tetraethyllead, Pb(C2H5)4, dissolve zinc and antimony mirrors.
5. The chemical changes that occur when solutions (and also gases) are exposed
to high-energy radiation also appear to involve the transient formation of
free radicals.
6. Terephthalic acid combines with ethylene glycol which on condensation
forms a polymer molecule known as dacron.
7. Styrene is an aromatic compound which on polymerisation gives polystyrene.
8. Silicon consists of very large groups silicon atoms joined together through
an oxygen atom. The linkage –Si–O–Si–O–Si– seems to be very stable
compounds in which the silicon-oxygen bond occurs and in which the
remaining valences are filled by hydrogens are called siloxanes.
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Material 203
Kinetics and Mechanism 9. Cationic or carbonium polymerization involves the formation of a carbonium
Polymerization
10. Catalyst for carbanion polymerization include, alkali metals, alkali metal
NOTES amides, alkoxides, alkyls, aryls, hydroxides and cyanides.
10.5 SUMMARY
 Radical, also called Free Radical, in chemistry, molecule contains at least

one unpaired electron. Most molecules contain even numbers of electrons,
and the covalent chemical bonds holding the atoms together within a molecule
normally consist of pairs of electrons jointly shared by the atoms linked by
the bond.
 Most radicals may be considered to have arisen by cleavage of
normal electron-pair bonds, every cleavage having produced two separate
entities, each of which contains a single, unpaired electron from the broken
bond .
 Certain free radicals are stabilized by their peculiar structures; they exist for
appreciable lengths of time, given the right conditions. Most free radicals,
however, including such simple ones as the methyl (·CH3) and ethyl (·C2H5)
radicals, are capable of only the most fleeting independent existence.
 Stable radicals is the first relatively stable free radical, triphenylmethyl
(structure I), was discovered by Moses Gomberg in 1900. In
this compound the central carbon is trivalent since it is combined with three
substituents instead of four, and its unshared electron is represented by a
dot.
 The vapours of tetramethyllead, Pb(CH3)4, mixed with gaseous hydrogen,
H2, were passed through a silica tube at low pressure. When a portion of
the tube was heated to about 800° C, the tetramethyllead was decomposed
and a mirror of metallic lead deposited on the internal surface of the tube.
 The existence of the various known unstable free radicals is most commonly
from tetraethyllead, Pb(C2H5)4, dissolve zinc and antimony mirrors.
 Free radicals, however, are paramagnetic (attracted by a magnet) because
of the spin of the odd electron, the spins of the remaining paired electrons
effectively canceling each other.
 Free radical polymerization consists of three fundamental steps, initiation,
propagation, and termination.
 Styrene is an aromatic compound which on polymerisation gives polystyrene.
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 Ordinary glass has the weakness of being brittle. The development of clear Kinetics and Mechanism
Polymerization
transparent high polymers is certainly one of the may achievements in polymer
chemistry.
 Methyl methacrylate readily polymerises yielding a clear transparent glass.
NOTES
This polymer, which is sold under trade names such as plexiglas and lucite
may be made into sheets or various articles as desired.
 Terephthalic acid combines with ethylene glycol which on condensation
forms a polymer molecule known as dacron.
 In organisilicon polymers silicon is directly below carbon in the periodic
table, but the chief interest in silicon has been with respect to natural silicates
in silica and in glasses. The fact that silicon forms hydrides of the type Sin
H2n+2.
 Silicon consists of very large groups silicon atoms joined together through
an oxygen atom. The linkage –Si–O–Si–O–Si– seems to be very stable
compounds in which the silicon-oxygen bond occurs and in which the
remaining valences are filled by hydrogens are called siloxanes.
 Ionic polymerizations tend to be very rapid even at low temperatures. The
polymerization of isobutylene with AlCl3 or BF3 is carried out commercially
at —100ºC and an estimate of the life-time of a growing chain of isobutylene
in this case is about 10–6 sec, much shorter than the usual life time of a free-
radical chain.
 Cationic or carbonium polymerization involves the formation of a carbonium
 Catalyst for carbanion polymerization include, alkali metals, alkali metal
amides, alkoxides, alkyls, aryls, hydroxides and cyanides.
10.6 KEY WORDS
 Propagation: Propagation is the growth of a polymer chain by successive

addition of monomers.
 Unstable Radicals: Unstable Radicals are simple free radicals such
as methyl, ·CH3, also exist and play key roles as transient intermediates in
many chemical reactions.
 Stable Radicals: Stable Radicals is the first relatively stable free
radical, triphenylmethyl (structure I), was discovered by Moses Gomberg in
1900. In this compound the central carbon is trivalent since it is combined
with three substituents instead of four, and its unshared electron is represented
by a dot.
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Material 205
Kinetics and Mechanism  Dacron: Terephthalic acid combines with ethylene glycol which on
Polymerization
condensation forms a polymer molecule known as dacron.
 Styrene: Styrene is an aromatic compound which on polymerisation gives
NOTES polystyrene.

EXERCISES

1. What are free radicals?
2. Brief a note on stable radicals.
3. What are unsatable radicals?
4. Give a brief account on magnetic properties of free radicals.
5. Brief a note on mechanism of free radical polymerization.
6. Write a short note on ionic polymerization.
7. What is anionic polymerization ?
1. Explain in detail about free radicals and its types.
2. Distinguish between stable and unstable radicals.
3. Discuss the magnetic properties of free radicals.
4. Describe in detail the mechanism of free radical polymerization and the
steps involved in it.
5. Write a detailed note on cationic and anionic polymerization.
6. Distinguish between cationic and anionic polymerization.

& Company Ltd.
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Polymerization
UNIT 11 POLYMERIZATION Techniques
TECHNIQUES
NOTES
Structure
11.0 Introduction
11.1 Objectives
11.2 Methods of Polymerization
11.4 Summary
11.5 Key Words
11.0 INTRODUCTION
Polymerization is the process in which relatively small molecules, called monomers,
three, or more different compounds. Broadly polymerization can be classified into
two categories, i.e., step-growth or condensation polymerization and chain-growth
or addition polymerization
Polymerization reaction takes place in matter-solid, liquid, gas. The solid
state reactions are usually slow, they are not considered practical for this reason.
The gas-phase reactions do take place but normally they require maintenance of
high temperatures, a condition in which almost all high molecular weight polymers
become unstable. Hence almost all commercial process of polymerization are liquid
phase reactions. It is of two types which are further classified as follows;
homogenous type which includes bulk polymerization/ mass polymerization and
solution polymerization, while heterogeneous type includes emulsion polymerization
and suspension polymerization/pearl/bead polymerization. The homogenous or
heterogeneous terms refers only to initial conditions of the system and are not to
the subsequent conditions. Hence the concept of homogeneity or heterogeneity is
based on only the initial conditions of the system.
In this unit, you will study about polymerization and the various methods of
polymerization.
11.1 OBJECTIVES
 Understand what polymerization is
 Explain the various methods of polymerization
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Material 207
Polymerization
Techniques 11.2 METHODS OF POLYMERIZATION
Polymerization is the process in which relatively small molecules, called monomers,
NOTES
three, or more different compounds. Usually at least 100 monomer molecules
must be combined to make a product that has certain unique physical properties,
such as elasticity, high tensile strength, or the ability to form fibres that differentiate
polymers from substances composed of smaller and simpler molecules often, many
thousands of monomer units are incorporated in a single molecule of a polymer.
The formation of stable covalent chemical bonds between the monomers sets
polymerization apart from other processes, such as crystallization, in which large
numbers of molecules aggregate under the influence of weak intermolecular forces.
Broadly polymerization can be classified into two categories:
 Chain-Growth or Addition Polymerization
 Step-Growth or Condensation Polymerization
Chain-Growth or Addition Polymerization
As the name suggests addition polymers form when an addition reaction occurs.
The repeating monomers form a linear or branch structure depending on the type
of monomer. During addition polymerization, the monomers rearrange themselves
to form a new structure. But there is no loss of an atom or a molecule. Again there
are four types of addition polymerizations which are:
 Free Radical Polymerization: Here the addition polymer forms by addition
of atoms with a free electron in its valence shells. These are known as free
radicals. They join in a successive chain during free radical polymerization.
 Cationic Polymerization: A polymerization where a cation is formed
causing a chain reaction. It results in forming a long chain of repeating
monomers
 Anionic Vinyl Polymerization: Involves the polymerization of particularly
vinyl polymers with a strong electronegative group to form a chain reaction’
 Coordination Polymerization: This method was invented by two scientists
Ziegler and Natta who won a Nobel Prize for their work. They developed
a catalyst which let us control the free radical polymerization. It produces a
polymer which has more density and strength.
Step-Growth or Condensation Polymerization
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208 Material
Condensation polymers form from the step growth polymerization. Here Polymerization
Techniques
when molecules of monomers react to form a bond they replace certain molecules.
These molecules are the by-product of the reaction. In most cases, this by-product
is a water molecule.
The type of polymers that result from a condensation polymerization depends NOTES
on the monomers. If the monomer has only one reactive group, the polymers that
form have low molecular weight. When monomers have two reactive end groups
we get linear polymers. And monomers with higher than two reactive groups results
in a polymer with a three-dimensional network.
Polyester and nylon are two common condensation polymers. Even Proteins and
Carbohydrates are a result of condensation polymerization.
Addition Polymerization vs. Condensation Polymerization
A comparative analysis of the two types of polymerization to understand them
better is as follows:
 In addition polymerization monomers only join at the active site of the chain.
But in condensation polymerization, any molecule can react with any other.
 In addition polymerization, there are three distinct steps. Initiation,
propagation and finally termination. In condensation polymerization, there
is no termination step. The end groups remain reactive through the entire
process.
 Addition polymerization results in homo-chain polymers whereas
condensation polymerization results in hetro-chain polymers.
 The most significant difference is that in addition polymers there is no loss of
atom. But in condensation reaction, there is a loss of a molecule of
water, ammonia etc as a by-product.
Polymerization reaction may take place in any of the three states of matter-
solid, liquid, gas. The solid state reactions are usually slow, they are not
considered practical for this reason. The gas-phase reactions do take place
but normally they require maintenance of high temperatures, a condition in which
almost all high molecular weight polymers become unstable. Hence almost all
commercial process of polymerization are liquid phase reactions.
Liquid-Phase Reactions:
Homogenous Type
 Bulk Polymerization/Mass Polymerization
 Solution Polymerization
Heterogeneous Type
 Emulsion Polymerization
 Suspension Polymerization/Pearl/Bead Polymerization
The homogenous or heterogeneous terms refers only to initial conditions of the
system and are not to the subsequent conditions. For example, Polymerization of
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Material 209
Polymerization vinyl chloride by mass polymerization method is considered a homogenous type
Techniques
of reaction, because initially the system is homogenous. But the polymer being in
compatible to the monomer phase, the system subsequently becomes
heterogeneous. Hence the concept of homogeneity or heterogeneity is based on
NOTES only the initial conditions of the system.
Mass/Bulk Polymerization
Bulk polymerization or mass polymerization is carried out by adding a soluble
initiator to pure monomer in liquid state. The initiator should dissolve in the monomer.
The reaction is initiated by heating or exposing to radiation. As the reaction proceeds
the mixture becomes more viscous. The reaction is exothermic and a wide range
of molecular masses are produced.
Bulk polymerization is carried out in the absence of any solvent or dispersant
and is thus the simplest in terms of formulation. It is used for most step-growth
polymers and many types of chain-growth polymers. In the case of chain-growth
reactions, which are generally exothermic, the heat evolved may cause the reaction
to become too vigorous and difficult to control unless efficient cooling.
In this type of polymerization the monomer is taken in liquid form. The
initiators, chain transfer agent-used to control the molecular weight are dissolved
in monomer. Now the system becomes homogenous. The reaction mass is heated
or exposed to a radiation source for the purpose of initiating the polymerization
reaction and is kept under agitation for proper heat and mass transfer.
As the polymerization proceeds the viscosity of the medium increases and mixing
becomes difficult leading to products with very broad molecular weight distribution.
There action is purely exothermic. Batch reactors are used for polymerization.
The phenomenon in which the molecular weight of a substance increase
tremendously is known as ‘Auto accleration’.
Advantages
Advantages of Mass/Bulk Polymerization includes,
 High purity
 High molecular weight and molecular weight distribution
 No solvent contamination
 Good flow characteristics
 Longer polymerization time for high molecular weight polymers (nearly 10-
16 hrs)
 Product can be used directly and no isolation is required due to its resistance
towards solvents
Disadvantages
Disadvantages of Mass/Bulk Polymerization includes,
 High viscosity
 Stirring becomes difficult after 30-40%conversion. As said above the mol.wt
Self-Instructional increases enormously which leads to auto acceleration
210 Material
 Due to gel effect/transdorff effect Rp is very high Polymerization
Techniques
 Heat removal is difficult.
 Hot spots may form and explosion may possible.
 Removal of last traces of unreacted monomer is difficult. NOTES
For reducing the disadvantages of bulk polymerization, the process can be
carried out in a solution. This is known as solution polymerization.
Polymer characterization is the analytical branch of polymer science.
The discipline is concerned with the characterization of polymeric materials on a
variety of levels. The characterization typically has as a goal to improve the
performance of the material. As such, many characterization techniques should
ideally be linked to the desirable properties of the material such as strength,
impermeability, thermal stability, and optical properties.
Characterization techniques are typically used to determine molecular mass,
molecular structure, morphology, thermal properties, and mechanical properties.
Applications
Applications of Mass/Bulk Polymerization includes;
 Casting PMMA sheets.
 Used in free radical polymerization of MMA or styrene to get moulding
powders.
Solution Polymerization
Solution polymerization is a method of industrial polymerization. In this procedure,
a monomer is dissolved in a non-reactive solvent that contains a catalyst. The
reaction results in a polymer which is also soluble in the chosen solvent. Heat
released by the reaction is absorbed by the solvent, and so the reaction rate is
reduced. Moreover the viscosity of the reaction mixture is reduced, not
allowing auto acceleration at high monomer concentrations. Once the maximum
or desired conversion is reached, excess solvent has to be removed in order to
obtain the pure polymer. Hence, solution polymerization is mainly used for
applications where the presence of a solvent is desired anyway, as is the case for
varnish and adhesives. It is not useful for the production of dry polymers because
of the difficulty of complete solvent removal. This process is one of two used in the
production of sodium polyacrylate, a super absorbent polymer used in
disposable diapers.
Notable polymers produced using this method are PolyAcrylo Nitrile (PAN)
and Poly Acrylic Acid (PAA). Solution polymerization is used to create polymers
and copolymers by dissolving a monomer and a catalyst in a non-reactive solvent.
During this process, the solvent liquid absorbs the heat generated by the chemical
reaction which controls the reaction rate. The liquid solvent used in the solution
polymerization procedure usually remains a solvent for the resulting polymer or
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Material 211
Polymerization copolymer. This process is only suitable for the creation of wet polymer types, as
Techniques
the removal of excess solvent is difficult. While removal of excess solvent is possible
using distillation, it is usually not considered economically possible in an industrial
situation.
NOTES The process of solution polymerization offers a few advantages as well as
one major disadvantage. The advantages include precise control of the chemical
reaction, control of the resulting heat and viscosity, and control over auto
acceleration of the process. The disadvantage of the process is the difficulty involved
in the removal of excess solvent from the finished polymer.
The solvents used in the solution polymerization procedure must be chosen
carefully. A solvent that is non-reactive to the monomer is essential to the process.
If a reactive solvent is used, dangerous chain reaction processes or other undesirable
effects can occur as a result of auto acceleration. Auto acceleration is a reaction
that occurs when the heat produced by polymerization does not dissipated quickly
enough by the solvent. As the heat builds up, the viscosity of the solution increases,
causing the polymerization process to accelerate beyond safe control.
Industrial solution polymerization processes are commonly used to produce
polymers with special characteristics. The chemical reaction that takes place
between the monomer and catalyst can lend unique properties to the end product.
One example of this type of polymer is sodium polyacrylate, the exceptionally
absorbent polymer used in disposable diapers.
While this process is not generally feasible for dry polymers, it works well
for wet polymer types. The process of industrial solution polymerization is used to
create polymers and copolymers that can be used in their solution form. Examples
of this usage include industrial glues and surface coatings.
Synthetic elastomers can also be produced using the solution polymerization
process. This method produces a more precise polymer than emulsion
polymerization methods. By controlling the addition of refined monomers to the
catalyst-solvent solution, the resulting polymers can be carefully designed for specific
properties. These synthetic elastomers are commonly found in products such as
latex gloves, neoprene wet suits and floor covering materials.
Monomer is dissolved in suitable solvent along with chain transfer agents
and initiators (free radical initiator). Catalyst may be ionic or co-ordination catalyst
which can either dissolved or suspended. The presence of inert solvents medium
helps to control viscosity, increase and promote proper heat transfer. Process
maybe continuous/batch wise operation. The product obtained is in liquid phase.
For most cases water is taken as solvent.
Advantages
Advantages of Solution Polymerization includes,
 Heat transfer easy due to presence of solvent
 Stirring is easy because the solution is low viscous
 Mass transfer is easy
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 The product obtained is in liquid form and can be directly used for applications Polymerization
Techniques
such as adhesives
Disadvantages
Disadvantages of Solution Polymerization includes, NOTES
 High mol.wt polymers cannot be manufactured by this process because
addition of solvent lowers monomer concentration which lowers rate of
polymerization
 Complete removal of solvent is more difficult
 Polymer obtained is Impure
 Requires drying to be used as solid
Applications
Applications of Solution Polymerization includes,
 Widely used for coating and adhesives.
 Industrial production of PAN by free radical polymerization.
 Polyisobutylene by cationic polymerization use this technique.
Emulsion Polymerization
Emulsion polymerization is a type of radical polymerization that usually starts with
an emulsion incorporating water,monomer, and surfactant. The most common type
of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer
(the oil) are emulsified (with surfactants) in a continuous phase of water. Water-
soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses,
can also be used to act as emulsifiers/stabilizers. The name ‘emulsion polymerization’
is a misnomer that arises from a historical misconception. Rather than occurring in
emulsion droplets, polymerization takes place in the latex particles that form
spontaneously in the first few minutes of the process. These latex particles are
typically 100 nm in size, and are made of many individual polymer chains. The
particles are stopped from coagulating with each other because each particle is
surrounded by the surfactant (soap); the charge on the surfactant repels other
particles electrostatically. When water-soluble polymers are used as stabilizers
instead of soap, the repulsion between particles arises because these water-soluble
polymers form a ‘hairy layer’ around a particle that repels other particles, because
pushing particles together would involve compressing these chains.
Emulsion polymerization is used to manufacture several commercially
important polymers. Many of these polymers are used as solid materials and must
be isolated from the aqueous dispersion after polymerization. In other cases the
dispersion itself is the end product. A dispersion resulting from emulsion
polymerization is often called a latex (especially if derived from asynthetic rubber)
or an emulsion (even though ‘emulsion’ strictly speaking refers to a dispersion of
an immiscible liquid in water). These emulsions find applications in adhesives, paints,
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Polymerization paper coating and textile coatings. They are often preferred over solvent-based
Techniques
products in these applications due to the absence of VOCs (Volatile Organic
Compounds) in them.
This technique suits well for addition polymerization. In this type apart from
NOTES dispersed particles and dispersion media several other components are added.
Usually the dispersion media is water. The monomer is dispersed in water in the
form of small droplets of diameter 1m. These droplets have the natural tendency
to coalesce and gradually become larger and forms immiscible layer. In order to
discourage this tendency emulsifying agents such as soap like materials are added.
Apart from that surface tension regulators, buffers, protective colloids are added
to prevent pre-mature coalescence and precipitation of droplets of monomer as
well as those of partially polymerized polymer by preventing adhesion of sticky
drops.
Mechanism involved in Emulsion Polymerization
Emulsifying agent  Sodium or potassium salts of organic fatty acids (soap) and
sulphates
Emulsifying agent are spermatozoa like representation includes inorganic
head (hydrophilic in nature) and organic tail (hydrophobic in nature). The emulsifying
agents are substances with very low solubility in medium and therefore as its
concentration is increased, the molecularly dispersed substances begins to form
molecular aggregates known as micelles which exists either in spherical form or
thin layer. In micelles because of their hydrophilic and hydrophobic characteristics,
the molecules orient themselves so as to have the tails towards centre and head
towards water phase. They have average dimensions of order 50-60Å. The
concentration of emulsifying agent at which ion like molecules begin to form micelle
is called Critical Micelle Concentration (CMC) which changes the rate of change
of physical properties
Fig. 11.1 Mechanism Involved in Emulsion Polymerization
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When monomer is added which is organic in nature prefers the interior of the Polymerization
Techniques
micelle because of organic environment. Micelle has the tendency to contract
because of surface tension. Hence the migration of monomer from monomer
droplets to the interiors of micelle continues till equilibrium is reached between
swelling and contracting tendencies. When initiators are decomposed in NOTES
water phase it bounces around the solution to create radicals. At this point the
surface area presented by monomer-swollen micelle is much greater than monomer
droplets so the probability for radicals to enter the monomer swollen micelle is
very high. When the radicals enter the micelle it initiates the reaction.
When polymerization takes place within micelle it lowers the concentration of
monomer so that a gradient is established between monomer which in uninitiated
and initiated one both diffuse. Thus the uninitiated monomer swollen micelles
gradually disappear losing their monomer content. When a second radical find its
way into the micelle, for the conditions prevailing within the micelle the rate of
termination is much greater than the rate of propagation. Hence chain terminates
eventually and remains until a third radical enters, initiating the growth of second
chain and so on.
Advantages
Advantages of Emulsion Polymerization includes,
 No chain transfer problem and heat transfer problem. The products obtained
in the form of latex are directly usable
 Very high mol.wt can be obtained in very less time nearly 1-2 hours, high
average chain lengths are achievable
 Suitable for ionic/radical condensation
 High molecular weight polymers can be made at fast polymerization rates.
By contrast, in bulk and solution free radical polymerization, there is a trade
off between molecular weight and polymerization rate
 The continuous water phase is an excellent conductor of heat, enabling fast
polymerization rates without loss of temperature control
 Since polymer molecules are contained within the particles, the viscosity of
the reaction medium remains close to that of water and is not dependent on
molecular weight
 The final product can be used as is and does not generally need to be
altered or processed
Disadvantages
Disadvantages of Emulsion Polymerization includes,
 Because of several additives added to the system the product obtained in
less pure when compared to bulk polymerization
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Polymerization  To recover the polymer in the solid form considerable technology is needed
Techniques
 Use of very large quantities of water lowers the yield per reactor volume
 Surfactants and other polymerization adjuvants remain in the polymer or
NOTES are difficult to remove
 For dry (isolated) polymers, water removal is an energy-intensive process
 Emulsion polymerizations are usually designed to operate at high conversion
of monomer to polymer. This can result in significant chain transfer to polymer.
 Can not be used for condensation, ionic or Ziegler-Natta polymerization,
although some exceptions are known.
Applications
Applications of Emulsion Polymerization includes,
 Most widely used industrial technique and monomers such as vinyl chloride,
butadiene, chloroprene, vinyl acetate, acrylates are polymerized by this
technique
 Suitable for producing very high mol.wt products
Suspension Polymerization
Suspension polymerization is used only in free radical type processes. The monomer
is mechanically dispersed in a media, usually water. There are cases where an
organic media is used in which neither the polymer nor the monomer are soluble in
the organic media.
 Styrene, i.e., liquid
 Vinyl Chloride, i.e., gas at room temperature
For suspension polymerization, there are two phases, water and organic, and the
starting point may be 10 parts of the former, and 1 part of the latter. The initiator
used can be water soluble or organic soluble [benzoyl peroxide, AIBN, or
(NH4)2(SxO4)y.] Usually the initiator is organic soluble.
When using gases, pressure and containment concerns exist
 There are two separate phases throughout the whole process.
 The droplets must be kept far apart.This requires agitation: consistent,
efficient, and controlled. A suspending agent can be used. Poly(vinyl alcohol)
dissolved in the aqueous phase is a typical suspending agent.
 The rate of suspension polymerization is similar to the rate of bulk
polymerization, but the heat transfer is much better. For suspension
polymerization, initiation, propogation, and termination take place inside
the droplet.
 Examples include the polymerization of methyl methacrylate, and vinyl
chloride.
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 The solution polymerization of butadiene, isobutylene and isoprene require Polymerization
Techniques
a pressure system.
 The media to monomer ratio is 10:1. Is this wt/vol, wt/wt, or vol/vol?? In an
industrial setting it may be easier to combine chemical feedstocks on a per
NOTES
volume basis.
 Particle size is affect by the following four factors:
o Stirring Rate
o Ratio of Reactants
o Suspension Agent
o Temperature
 The plant operator must control temperature, and the particle size (of the
growing polymer mass in the bubble.) If the particle size gets to large, the
particle will absorb too much heat. This probably relates to the idea that as
you increase the volume of a sphere, the ratio of surface area to volume
decreases, and this ratio relates to heat transfer. Particle size may be 0.01
to 0.5 cm, or as low as 1 micron.
A suspension agent is a material that gives a surface activation that keeps droplets
from become larger (droplets coming together to form larger droplets is
called coalescence).
The term coalescence is also used for when the polymer molecules in a
solution come together as the solvent evaporates, an example of which is the film
formation that occurs for a paint system.
Suspension polymerization is similar to bulk polymerization, and it could be
considered ‘bulk polymerization within a droplet’. The speed at which the reaction
takes place for a given temperature is the same, and just as for bulk polymerization,
the kinetics or rates are proportional to monomer concentration. There is efficient
heat transfer with speed or bulk process.
Recovery of product by mechanical separation (i.e, filtration, washing) is a
lot cheaper than thermo distillation. (this sentence sort of doesn’t make sense.)
The properties of the polymer are similar to those of the same polymer made by a
bulk polymerization.
Limitations
Limitations of Suspension Polymerization includes,
 It only applies to free radical process.
 Ionic catalysts do not work because they compete with water.
 Agitation is critical because as the viscosity within the bead rises, the reaction
rate increases suddenly (Tromsdoiff effect). This leads to a surge in heat
generation which does not usually occur in solution or emulsion
polymerization.
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Polymerization This method is employed to overcome some of the disadvantages of emulsion
Techniques
polymerization, for example the tendency of small polymer particles to adsorb
impurities. The size of monomer dispersed is greater compared to
emulsion polymerization. Here the monomer is insoluble in dispersion medium.
NOTES Initiator, suspension stabilizer are dispersed in water or inert organic liquids provided
the monomer and polymer is insoluble in it. The mechanism is similar to mass and
solution polymerization. Unlike in emulsion polymerization where close,intimate
contact between the two phases is established by emulsifying agent, each bead or
pearl of the monomer in suspension polymerization acts as minute,discrete mass
polymerization system. A protective colloid which is inert with respect to the
polymerization reaction and which increase the viscosity of the continuous phase
is added so that it would hydro dynamically hinder the coalescence of monomer
droplets. A protective colloid such as Magnesium carbonate is insoluble is
the solution and collects at the droplet-water interface by surface tension and
prevents the coalescence of drops upon collision.
Advantages
Advantages of Suspension Polymerization includes,
 No chain transfer problem
 No mass transfer problem
 No heat transfer problem
 Stirring is easy
 The product obtained is in granular form which is convenient to handle,
isolation is easy
Disadvantages
Disadvantages of Suspension Polymerization includes,
 Only water insoluble monomers are used
 Emulsifier is needed to wash the suspending agents
 Purity is less when compared to polymer that obtained by mass
polymerization
 Yield is low when compared to mass polymerization
 Requires long time for very high conversions
Applications
Applications Suspension Polymerization includes,
 Expandable polystyrene beads, styrene-divinylbenzene copolymer beads
used in preparation of ion exchange resins are produced
 PVA beads are produced by this technique using free radical initiators
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Polymerization
Techniques
Check Your Progress
1. Define polymerization.
2. In how many categorizes polymerization classified? NOTES
3. How is mass polymerization is carried out?
4. Give the advantages of mass polymerization.
5. What is solution polymerization?
6. List the disadvantages of solution polymerization.
7. What are the applications of emulsion polymerization.

QUESTIONS
1. Polymerization is the process in which relatively small molecules,
2. Polymerization is classified into two categories:
 Step-Growth or Condensation Polymerization
 Chain-Growth or Addition Polymerization
3. Bulk polymerization or mass polymerization is carried out by adding a
soluble initiator to pure monomer in liquid state. The initiator should dissolve
in the monomer. The reaction is initiated by heating or exposing to radiation.
As the reaction proceeds the mixture becomes more viscous. The reaction
is exothermic and a wide range of molecular masses are produced.
4. Advantages of Mass/Bulk Polymerization includes:
 High purity
 High molecular weight and molecular weight distribution
 No solvent contamination
 Good flow characteristics
 Longer polymerization time for high molecular weight polymers (nearly
10-16 hrs)
 Product can be used directly and no isolation is required due to its
resistance towards solvents.
5. Solution polymerization is a method of industrial polymerization. In this
procedure, a monomer is dissolved in a non-reactive solvent that contains a
catalyst. The reaction results in a polymer which is also soluble in the chosen
solvent. Heat released by the reaction is absorbed by the solvent, and so
the reaction rate is reduced.
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Polymerization 6. Disadvantages of Solution Polymerization includes:
Techniques
 High mol.wt polymers cannot be manufactured by this process because
addition of solvent lowers monomer concentration which lowers rate
of polymerization
NOTES
 Complete removal of solvent is more difficult
 Polymer obtained is Impure
 Requires drying to be used as solid
7. Applications of Emulsion Polymerization includes:
 Most widely used industrial technique and monomers such as vinyl
chloride, butadiene, chloroprene, vinyl acetate, acrylates are
polymerized by this technique
 Suitable for producing very high mol.wt products
11.4 SUMMARY
 Polymerization is the process in which relatively small molecules,

network molecule, called a polymer. The monomer molecules may be all
alike, or they may represent two, three, or more different compounds.
 The formation of stable covalent chemical bonds between the monomers
sets polymerization apart from other processes, such as crystallization, in
which large numbers of molecules aggregate under the influence of weak
intermolecular forces.
 Broadly polymerization can be classified into two categories: step-growth
or condensation polymerization and chain-growth or addition polymerization
 In addition polymers the repeating monomers form a linear or branch
structure depending on the type of monomer. During addition polymerization,
the monomers rearrange themselves to form a new structure.
 In free radical polymerization the addition polymer forms by addition of
atoms with a free electron in its valence shells. These are known as free
radicals. They join in a successive chain during free radical polymerization.
 In cationic polymerization a cation is formed causing a chain reaction. It
results in forming a long chain of repeating monomers.
 In anionic vinyl polymerization the polymerization of particularly vinyl
polymers with a strong electronegative group to form a chain reaction’
 Condensation polymers form from the step growth polymerization. Here
when molecules of monomers react to form a bond they replace certain
molecules. These molecules are the by-product of the reaction. In most
cases, this by-product is a water molecule.
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 In addition polymerization monomers only join at the active site of the chain. Polymerization
Techniques
But in condensation polymerization, any molecule can react with any other.
 Bulk polymerization is carried out in the absence of any solvent or dispersant
and is thus the simplest in terms of formulation. It is used for most step-
NOTES
growth polymers and many types of chain-growth polymers.
 Polymer characterization is the analytical branch of polymer science.The
discipline is concerned with the characterization of polymeric materials on a
variety of levels. The characterization typically has as a goal to improve the
performance of the material.
 Solution polymerization is a method of industrial polymerization. In this
procedure, a monomer is dissolved in a non-reactive solvent that contains a
catalyst. The reaction results in a polymer which is also soluble in the chosen
solvent. Heat released by the reaction is absorbed by the solvent, and so
the reaction rate is reduced.
 The liquid solvent used in the solution polymerization procedure usually
remains a solvent for the resulting polymer or copolymer. This process is
only suitable for the creation of wet polymer types, as the removal of excess
solvent is difficult.
 The solvents used in the solution polymerization procedure must be chosen
carefully. A solvent that is non-reactive to the monomer is essential to the
process. If a reactive solvent is used, dangerous chain reaction processes
or other undesirable effects can occur as a result of auto acceleration.
 Emulsion polymerization is used to manufacture several commercially
important polymers. Many of these polymers are used as solid materials
and must be isolated from the aqueous dispersion after polymerization. In
other cases the dispersion itself is the end product.
11.5 KEY WORDS
 Polymerization: Polymerization is the process in which relatively

small molecules, called monomers, combine chemically to produce a very
large chain like or network molecule, called a polymer.
 Free radical polymerization: In free radical polymerization the addition
polymer forms by addition of atoms with a free electron in its valence shells.
These are known as free radicals. They join in a successive chain during
free radical polymerization.
 Cationic polymerization: A polymerization where a cation is formed
causing a chain reaction. It results in forming a long chain of repeating
monomers.
 Anionic vinyl polymerization: Involves the polymerization of particularly
vinyl polymers with a strong electronegative group to form a chain reaction’
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Polymerization  Suspension agent: A suspension agent is a material that gives a surface
Techniques
activation that keeps droplets from become larger (droplets coming together
to form larger droplets is called coalescence).
NOTES
EXERCISES

1. What is polymerization?
2. What is addition polymerization?
3. Give the advantages and disadvantages of bulk polymerization.
4. How is solution polymerization conducted?
5. What are the disadvantages of emulsion polymerization ?
6. Brief a note on suspension polymerization.
1. Explain in detail about polymerization and its types.
2. Distinguish between addition polymerization and condensation
polymerization.
3. Write a elaborated note on mass polymerization mentioning its advantages,
disadvantages, characterization and applications.
4. Discuss about solution polymerization giving its advantages, disadvantages,
and applications.
5. Explain what is emulsion polymerization, also talk about its mechanism,
advantages, disadvantages, and applications.
6. Give a elaborated note on suspension polymerization mentioning about its
limitations, advantages, disadvantages, and applications.

& Company Ltd.
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Colloids
BLOCK - IV
COLLOIDS AND SOLAR ENERGY
NOTES
UNIT 12 COLLOIDS
Structure
12.0 Introduction
12.1 Objectives
12.2 Colloids: Classification, Stability and Properties
12.2.1 Classification of Colloids
12.2.3 The Stabilisation of the Colloidal State
12.4 Summary
12.5 Key Words
12.0 INTRODUCTION
In chemistry, a colloid is a mixture in which one substance of microscopically

dispersed insoluble particles is suspended throughout another substance.
Sometimes the dispersed substance alone is called the colloid; the term colloidal
suspension refers unambiguously to the overall mixture. Unlike a solution,
whose solute and solvent constitute only one phase, a colloid has a dispersed phase
and a continuous phase .
The dispersed-phase particles have a diameter between approximately 1
and 1000 nanometers. Such particles are normally easily visible in an optical
microscope, although at the smaller size range (r < 250 nm), an ultramicroscope or
an electron microscope may be required.
Some colloids are translucent because of the Tyndall effect, which is the
scattering of light by particles in the colloid. Other colloids may be opaque or have
a slight color.
In this unit, you will study about colloids, its classification, stability and
properties.
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Colloids
12.1 OBJECTIVES
NOTES  Understand what colloids are
 Discuss the classification, stability and properties of colloids
12.2 COLLOIDS: CLASSIFICATION, STABILITY

AND PROPERTIES
Colloids, in chemistry, are a mixture of two substances, in which one substance is
divided into minute particles aka colloidal particles (ranging from 1 to 1000 nm in
diameter) and dispersed or suspended over another substance. These insoluble
particles are inseparable either by filtering or centrifuging. Types of Colloids are
Sol, Emulsion, Foam, and Aerosol.
A colloid is a mixture in which one substance of microscopically dispersed
insoluble particles are suspended throughout another substance. Sometimes the
dispersed substance alone is called the colloid. The colloid consists of a dispersed
phase and a continuous phase. Unlike solutions, colloids do not constitute a solute
dissolved in the solvent phase. Rather, the solute phase is dispersed in the solvent
phase.The dispersed-phase particles have a diameter between approximately 1
and 1000 nanometers. Such particles are normally easily visible in an optical
microscope, although at the smaller size range (r< 250 nm), an ultramicroscope or
an electron microscope may be required.
Some colloids are translucent because of the Tyndall effect, which is the
scattering of light by particles in the colloid. Other colloids may be opaque or have
a slight color.
In other words it can be said that colloid are any substance that consists of
particles substantially larger than atoms or ordinary molecules but too small to be
visible to the unaided eye; more broadly, any substance, including thin films and
fibres, having at least one dimension in this general size range,
which encompasses about 10–7 to 10–3cm. Colloidal systems may exist as
dispersions of one substance in another—for example, smoke particles in air—or
as single materials, such as rubber or the membrane of a biological cell.
Colloids are generally classified into two systems, reversible
and irreversible. In a reversible system the products of a physical or chemical
reaction may be induced to interact so as to reproduce the original components.
In a system of this kind, the colloidal material may have a high molecular weight,
with single molecules of colloidal size, as in polymers, polyelectrolytes, and proteins,
or substances with small molecular weights may associate spontaneously to form
particles (for example, micelles, microemulsion droplets, and liposomes) of colloidal
size, as in soaps, detergents, some dyes, and aqueous mixtures of lipids. An
irreversible system is one in which the products of a reaction are so stable or
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are removed so effectively from the system that its original components cannot be Colloids
reproduced. Examples of irreversible systems include sols (dilute suspensions),

pastes (concentrated suspensions), emulsions, foams, and certain varieties of gels.
The size of the particles of these colloids is greatly dependent on the method of
preparation employed. NOTES
All colloidal systems can be either generated or eliminated by nature as well
as by industrial and technological processes. The colloids prepared in living
organisms by biological processes are vital to the existence of the organism. Those
produced with inorganic compounds in the Earth and its waters and atmosphere
are also of crucial importance to the well-being of life-forms.
The scientific study of colloids dates from the early 19th century. Among
the first notable investigations was that of the British botanist Robert Brown. During
the late 1820s Brown discovered, with the aid of a microscope, that minute particles
suspended in a liquid are in continual, random motion. This phenomenon, which
was later designated Brownian motion, was found to result from the irregular
bombardment of colloidal particles by the molecules of the surrounding
fluid. Francesco Selmi, an Italian chemist, published the first systematic study of
inorganic colloids. Selmi demonstrated that salts would coagulate such colloidal
materials as silver chloride and Prussian blue and that they differed in their
precipitating power. The Scottish chemist Thomas Graham, who is generally
regarded as the founder of modern colloid science, delineated the colloidal state
and its distinguishing properties. In several works published during the 1860s,
Graham observed that low diffusivity, the absence of crystallinity, and the lack of
ordinary chemical relations were some of the most salient characteristics of colloids
and that they resulted from the large size of the constituentparticles.
The early years of the 20th century witnessed various key developments
in physics and chemistry, a number of which bore directly on colloids. These
included advances in the knowledge of the electronic structure of atoms, in the
concepts of molecular size and shape, and in insights into the nature of solutions.
Moreover, efficient methods for studying the size and configuration of colloidal
particles were soon developed—for example, ultra centrifugal analysis,
electrophoresis, diffusion, and the scattering of visible light and X-rays. More
recently, biological and industrial research on colloidal systems has yielded much
information on dyes, detergents, polymers, proteins, and other substances important
to everyday life.
A solution consists of two components—a solute and a solvent. If a solution of
ferric chloride is poured into boiling water, a clear deep brown liquid is obtained.
The change in colour shows that a chemical reaction has occurred; in fact ferric
oxide has been formed. The latter is practically insoluble in water and would
normally precipitate but if formed under the right conditions, it may remain dispersed
throughout the liquid in the form of very small particles. The presence of these
particles is shown by the colour but they are not large enough to cause the liquid to
appear cloudy. This is an example of a colloidal system. In ordinary true solution,
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Colloids the solute is dispersed throughout the solvent in the form of single molecules or
ions. On the other hand, a suspension contains particles that are large enough to
be seen by the naked eye or through the microscope. Colloids occupy an
intermediate position between true solutions on one hand and suspensions on the
NOTES other.
The word colloids is of Greek origin; the Greek word Kolla, meaning ‘glue’.
Thomas Grahm is usually regarded as the founder of colloid science.
It is obviously impossible to draw a boundary line between true solutions
and colloidal solutions. Colloidal behaviour can be connected with greatly increased
surface area compared with the volume as the size is reduced. The essential
properties of colloidal dispersions can be ascribed to the fact that the ratio of
surface area to volume of the particles is very large. In the true solution, the system
consists of one phase only and there is no true surface of separation between the
molecular particles of solute and solvent. The size of particles in colloidal state
ranges between 5 mm–200 mm. Ostwald regarded colloidal systems as
heterogeneous in character, consisting of two phases: (i) disperse phase and (ii)
dispersion medium.
Disperse phase refers to the phase forming the particles. Dispersion medium
is the medium in which dispersion of the particles takes place.
The colloidal dispersions are thermodynamically unstable and tend to
coagulate and precipitate on standing unless suitable precautions are taken. Since
both the disperse phase and dispersion medium may be solid, liquid or gaseous,
there can be several different types of colloidal system. No example of colloidal
dispersion of one gas in another gas is known. Various types of colloidal dispersions
known are given in Table 12.1.
Table 12.1 Types of colloidal dispersions
Dispersion Disperse phase Name Examples
medium
Gas Gas — Unknown
Liquid Aerosol Fog, mist, clouds
(of liquid)
Solid Aerosol Smoke
(of solid)
Liquid Gas Foam Whipped cream, beaten egg white.
Liquid Emulsion Dispersion of water in oil or oil in
water, milk
Solid Sols AgCl, Au, As2S3 or S, in water, cof-
fee, tea, paints
Solid Gas Solid foam Gases absorbed by charcoal, white
flower and white hair
Liquid Gels Jellies, minerals with liquid, cheese,
butter, pearls
Solid Solid sol Glasses coloured with dispersed met-
als, ruby, glass
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12.2.1 Classification of Colloids Colloids
Dispersed Phase and Dispersion Medium:

A colloid is a mixture in which one substance which has fine particles (dispersed
phase) mixed into another substance (dispersion medium). The particles of the
NOTES
colloids have a range from 1 to 1000 nm in diameter. The solution is called colloidal
dispersion because the particles of solutions do not mix or settle down. They are
dispersed in the solution.
The substances which are dispersed in the solution are called dispersed
phase, and the solution in which it is dispersed is called dispersion medium.
 A colloidal system in which the dispersion medium is a liquid or gas is called
sols. They are called hydrosols or aqual sols. If the dispersion medium is
water. When the dispersion medium is alcohol or benzene, they are
accordingly called alcohols or benzosol.
 Colloidal systems in which the dispersion medium is air are called aerosols.
 Colloids in which the dispersion medium is a solid are called gels, for
example, cheese etc. They have a more rigid structure. Some colloids, such
as gelatin, can behave both as a sol and a gel. At high temperature and
low concentration of gelatin, the colloids is hydrosol. But at low temperature
and high gelatin concentration, the hydrosol can change into a gel.
Types of Colloids
Colloids can be classified according to different properties of the dispersed phase
and medium.
Firstly, based on the types of particles of the dispersed phase, colloids can be
classified as:
 Multimolecular Colloids
 Macromolecular Colloids
 Associated Colloids
Multimolecular Colloids
When the dissolution of smaller molecules of substance or a large number of atoms
takes place, they combine to form a species whose size is in the range of colloidal
size. The species formed is known as the multimolecular colloids. For example,
Sulphur solution contains particles which have thousands of S8.
Macromolecular Colloids
In this type of colloids, the macromolecules form a solution with a suitable solvent.
The size of the particles of this macromolecular solution lies in the range of colloidal
particles size. Thus this solution is also known as the macromolecular colloids.
The colloids formed here are similar to that of the actual solution in many respects
and are very stable.
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Colloids Example: Starch, proteins, enzymes, and cellulose are the naturally occurring
macromolecular colloids whereas polyethene, synthetic rubber, etc. are the synthetic
macromolecules.
NOTES Associated Colloids

Some substances act as a strong electrolyte when they are in low concentrations,
but they react as colloidal sols when they are in high concentration. In higher
concentration, particles aggregate showing a colloidal behavior. These aggregated
particles are known as the micelles. They are also known as the associated colloids.
The formation of the micelles occurs above a particular temperature called the
Kraft Temperature (TK) and also above a specific concentration called the critical
micelle concentration. These colloids can be reverted by diluting it.
Examples of some associated colloids are soaps and synthetic detergents.
Examples of Colloids
Based on the physical state of the dispersion medium and of the dispersed phase,
colloids can be classified into:
 Foam
 Solid Foam
 Aerosol
 Emulsion
 Gel
 Solid Aerosol
 Sols
 Solid sols
The following Table 12.2 describes the types of colloids along with examples:
Table 12.2 Colloids and Its Types
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Depending Upon the State of Dispersed and Dispersion Medium Colloids
Depending upon the state of dispersed particles and the dispersion medium, the
following system of classification of colloids can be employed:
When the Dispersion Medium is Liquid NOTES
 Foams: When the dispersed medium is gas. Examples include whipped

cream, shaving cream, etc
 Emulsions: When the dispersed phase is liquid. Examples include milk,
mayonnaise, etc.
 Sol: When the dispersed phase is solid. Examples include blood, pigmented
ink, etc.
When the Dispersion Medium is Gaseous
 Liquid Aerosol: When the dispersed phase is liquid. Examples include
fog, mist, hair sprays, etc.
 Solid Aerosol: When the dispersed phase is solid. Examples include smoke,
ice cloud, etc.
When the Dispersion Medium is Solid
 Solid Foam: When the dispersed medium is gas. Examples include
styrofoam, pumice, etc
 Gel: When the dispersed medium is liquid. Examples include agar, gelatin,
etc
 Solid Sol: When the dispersed medium is solid. Examples include cranberry
glass
Based on the nature of the interaction between the dispersion medium and the
dispersed phase, colloids can be classified into
 Lyophilic
 Lyophobic
Lyophilic: If the dispersed phase has an affinity for the dispersion medium, the
colloid is called a lyophilic colloid. The words lyo and philic means ‘liquid’ and
‘loving’ respectively. Thus, even if the dispersed phase is separated from the
dispersion medium, they can readily be reconstituted by simply mixing them.
Moreover, they are difficult to coagulate due to their stable nature. They are also
known as intrinsic colloids. Examples are starch, rubber, protein, etc.
Lyophobic: If the dispersed phase has little or no affinity for the dispersion medium,
the colloid is called a lyophobic colloid. The words lyo and phobic means ‘liquid’
and ‘fearing’ respectively. Hence, they are liquid-hating. They are difficult to prepare
because the dispersed phase does not readily form a colloid with the dispersion
medium, they require some special methods. They are unstable and require
stabilizing agents for their preservation. They are also known as extrinsic colloids. Self-Instructional
Material 229
Colloids Examples are sols of metals like silver and gold, sols of metallic hydroxides, etc.
The important points of difference between the lyophilic sols and lyophobic solutions
are summarized in the Table 12.3 below:
Table 12.3 Difference between the Lyophilic Sols and Lyophobic Solutions
NOTES
Based on Nature of Interaction Between Dispersed Phase and

Dispersion Medium
Hydrophilic Colloids: These are water-loving colloids. The colloid particles are
attracted toward the water. They are also known as reversible sols. Examples
include Agar, gelatin, pectin, etc.
Hydrophobic Colloids: These are opposite in nature to hydrophilic colloids. The
colloid particles are repelled by water. They are also called irreversible sols.
Examples include Gold sols, clay particles, etc.
Colloidal solutions are known as sols. If the dispersion medium is water,
they are called ‘hydrosols’ or sometimes ‘aquasols.’ If in a liquid as dispersion
medium, the disperse phase is liquid, the colloidal solution is known as emulsion.
Dispersion of solids in liquids can be roughly divided into two categories
lyophobic and lyophilic sols. Lyophobic (solvent heating) sols have little attraction
between the disperse phase and dispersion medium. These are relatively less stable
as compared with lyophilic sols. On heating or cooling the lyophobic systems,
solids are obtained which cannot be reconverted into sols either by adding solvent
or by warming. Typical examples of this category of colloids are sols of metals,
sulphur and silver halides. Lyophilic (solvent loving) sols on the other hand are
systems in which the disperse phase shows some definite affinity for the medium.
Lyophilic sols are generally reversible and behave like true solutions to some extent,
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for example, gums starches and proteins. These substances are absorbed by the Colloids
disperse phase and are stabilized by strong solvation. Some of the important
characteristics of lyophobic and lyophilic sols are listed in Table 12.4.
Table 12.4 Characteristics of lyophobic and a lyophilic colloids
NOTES
Lyophobic colloids Lyophilic colloids
1. These are generally unstable, get easily 1. Very stable and are not easily
coagulated on adding electrolytes. coagutaled by electrolytes.
2. Irreversible in character. 2. Reversible.
3. Prepared by indirect methods. 3. Usually prepared by simple solution
methods.
4. Viscosity of colloidal dispersion is 4. These are highly viscous systems.
same as that of the solvent.
5. These are generally inorganic 5. Mostly organic materials, e.g.,
materials, i.e., metals, sulphides and starch, proteins, gums, etc.
oxide sols.
6. Carry electric charge and stability 6. Carry little or no charge.
depends on zeta potential.
Methods of Preparation of Colloidal Solutions

Certain types of small molecules are capable of associating in solution as a result
of their mutual intermolecular interactions to form clusters or aggregates of colloidal
dimensions, known as association colloids or micelles. Some important substances
which behave in this way are surface active agents, certain dyes (methylene blue)
and phospholipids (lecithins). Since solutions of macromolecules and association
colloids are true solutions and are thermodynamically stable, they are formed
spontaneously on mixing the solute and the solvent, and their preparation presents
some problems. Examples include the preparation of aqueous solutions of proteins
dextrin starch and the reconstitution of blood serum and plasma. The preparation
of concentrated solutions of agar and gelatin requires heating and such solutions
form gel on cooling.
There are two ways in which colloidal size particles can be obtained: (a) by
building up the particles from single molecules. The methods under this category
are known as condensation or aggregation methods. (b) by disintegrating down
the bulk material to the colloidal particles. Methods under this category are known
as the dispersion methods.
In preparing a colloidal solution, care must be exercised to see that the vessels
used should be thoroughly clean and the materials used should be pure.
Condensation in Methods: A supersaturated solution of the disperse phase
is prepared in the dispersion medium by carefully controlling the temperature and
keeping the concentration of disperse phase to below. The various methods used
here are:
1. Reduction Method: It has been used to prepare sols of metals, e.g.,
gold, silver and platinum. The method involves the reduction of solutions
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Material 231
Colloids of their soluble salts or oxides using different reducing agents. The reducing
agents employed for the purpose are fomaldehyde, hydrogen, carbon
monoxide, hydrazine, hydroxylamine, lamine, tannin, etc. Ostwald prepared
colloidal gold solution by reducing gold chloride. A few drops of 0.1 per
NOTES cent gold chloride solution were added to 100 ml of distilled water. The
gold chloride was neutralized with calculated amount of potassium
carbonate. A few drops of 0.1 per cent tannin were added and the solution
was warmed when a cherry-red gold sol was produced. Tannin has also
got some protective action.
2. Oxidation Method: Colloidal sulphur may be prepared by the oxidation
of hydrogen sulphide. Hydrogen sulphide is passed into a solution of sulphur
dioxide in water until all the odour of sulphur dioxide has been removed.
Sulphur sol is produced according to the following reaction:
2H2S + SO2 = 2H2O + 3S
3. Ionic Equilibria Method: When a solution of silver nitrate is added to a
very dilute solution of a chloride, the solution becomes slightly cloudy but
no precipitate forms. The reaction can be symbolized as follows:
Ag+ + Cl– = AgCl(s)
Arsenious sulphide sol is obtained by mixing solution of hydrogen sulphide
and arsenious oxide:
2As3+ + 3S2– = As2S3(s)
4. Hydrolysis Method: This method is used for preparing oxide and
hydroxide sols. Ferric oxide sol can be prepared by pouring a solution of
ferric chloride into a large volume of boiling water, the reaction being
2FeCl3 + 6H2O = Fe2O3.3H2O + 6HCl
5. Exchange of Solvent Method: In general if a substance A is soluble in
B but insoluble in C, the colloidal solution of A can be prepared if a solution
of A and B is added to an excess of C; the two solvents being miscible
with each other.
Sulphur is slightly soluble in alcohol but practically insoluble in water. Sulphur
sol can thus be prepared by pouring a saturated solution of sulphur in ethanol into
water.
Dispersion methods:
(i) Bredig’s arc Method: This process consists in striking an electric arc
between wires of platinum, gold or silver immersed in water as shown in Figure
12.1. At high temperature, the arc causes the metal to vaporise and the vapours
are condensed by water to form colloidal particles. Traces of sodium hydroxide
or potassium carbonate are necessary for the stability of the colloidal dispersion.
The vessel is cooled in ice. The method was used by Bredig to prepare sols of
gold and platinum.
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Colloids
NOTES
Fig. 12.1: Bredig’s arc method

(ii) Mechanical Dispersion method: This consists in breaking the material
down to the colloidal size. The solid and dispersion medium are fed between
grinding surfaces, usually concentric cones rotating at a high speed ( 7, 000
revolutions per minute). This device is known as ‘colloid mills.’
(iii) Peptization Method: It has been found that ionic solids containing a
small concentration of a common ion tend to break up spontaneously into colloidal
particles. This process is known as peptisation. For example, a precipitate of
silver iodide can be peptised by shaking with a dilute solution of either potassium
iodide or silver nitrate.
Purification of Colloidal Solutions

A sol prepared by any one of the above methods very often contains other materials
besides the colloidal particles. It is often desirable to remove these impurities,
particularly when they are electrolytes as they reduce the stability of the sol.
The methods used for the purification of a colloidal solution are: (1) Dialysis
and (2) Ultrafiltration.
1. Dialysis: This method makes use of the fact that there is a significant
difference in size between colloidal particles and the dissolved molecules or ions.
The sol is placed inside a dialyser which consists of a vessel open at both ends.
The one end can be covered by a parchment or cellophane membrane. The dialyser
is nearly filled with the colloidal solution and suspended in a vessel containing
distilled water. Crystalloid gets through and the colloidal particles are retained.
The water in the tank is changed periodically or continuously. Graham’s dialyser
used is shown in Figure 12.2. The process of dialysis can be quickened by applying
an electric field. This process is called electro-dialysis and is shown in Figure
12.3. The colloidal solution along with the unwanted electrolyte is placed between
two dialysing membranes and pure water in a compartment on each side. When a
high potential is applied. The ions migrate into the water leaving the pure colloidal
solution.
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Material 233
Colloids
NOTES
Fig. 12.2 Dialysis

The process of dialysis depends essentially on the character of the aggregates
involved, the nature of the fluid and the semipermeability of the membrane. The
various dialysers which are used are cellulose nitrate and cellulose acetate
membranes.
Fig. 12.3 Electro-Dialysis

2. Ultrafiltration: This is another important method for purifying sols. The
process of ultrafiltration is similar to the filtration of an ordinary precipitate except
with the difference that the membrane used here is designed in such a way that it
will permit the passage of only electrolytes and medium, and not of colloid particles.
Colloid particles thus can be separated in the form of a slime from medium
containing electrolytes. Such membranes are made by impregnating ordinary filter
paper with collodion or a regenerated cellulose such as cellophone or visking.
Other such membranes can be unglazed porcelain and finely sintered glass. Since
ultrafiltration membranes are of delicate constitution and can be easily broken,
they are generally supported on wire screens particularly when the liquid is being
passed through them under pressure. Ultrafiltration being a slow process can be
quickened by using pressure or suction.
1. Optical Properties: Sols exhibit characteristic optical properties. Particles
of the colloidal size range are too small to be seen even with a microscope
but they are large enough to scatter light. Tyndall however found that the
zone of scattered light was larger than the particle itself and could be seen in
the microscope or sometimes by the naked eye. Many sols are coloured
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234 Material
showing that light of certain wavelength is absorbed. This is also connected Colloids
with the size of the particles as shown in the case of gold sols which may be
red or blue depending upon the particle size. It is, however, possible to
locate the position by means of the light that it scatters using an instrument
called the Ultramicroscope as is shown in Fig. 12.4. NOTES
Fig 12.4 Arrangement of Ultramicroscope
An intense beam of light is passed through the sol and the scattered light is
observed through a microscope at right angles to the beam. The number of
particles can be counted and it is also possible to decide the shapes of the
particles roughly.
Assuming the colloidal particles to be spherical in shape and the density of
the substance in the colloidal state to be same as in the bulk, we can calculate
the mean radius r of the particles using the relation.
3bv
r =
4 n
where b is the number of grams of the dry substance present per cc of the
colloidal solution. The number of particles n present in vcc of the solution is
determined using the ultramicroscope, r is the density of the dry substance.
2. The Brownian Movement: Robert Brown in 1827 observed that pollen
grains executed a ceaseless random motion and travelled a zig-zag path. It
has been found that all colloidal particles execute this random zig-zag motion
when seen under the ultramicroscope.
Fig. 12.5 The Brownian movement
This motion of the colloidal particles is known as Brownian motion.

Wiener suggested that in colloidal particles, the Brownian motion was arising
out of molecular motion. The small colloidal particles are knocked about
the collision with the molecules of the dispersion medium.
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Material 235
Colloids 3. Electrical Properties of Colloids: All sol particles are found to be
electrically charged. When a hydrophobic sol is placed in an electric field,
the particles move in one direction or another. This shows that the colloidal
particles are electrically charged with respect to the dispersion medium.
NOTES This motion of colloid particles under the action of an electric field is called
electrophoresis. The potential gradient in volts per cm can be derived from
the applied emf and the dimensions of the apparatus. An electrophoretic
apparatus employed for this purpose is shown in Fig. 12.5. It consists of a
U-tube of the form shown. It is filled with ferric hydroxide sol, and then
distilled water is poured. A high potential is applied between electrodes
placed in the water, the boundary between the colloid and the distilled water
begins to move towards the cathode. This movement of colloid particles
under the action of electric field shows that colloids are charged particles. A
large majority of sols are negatively charged; some of the common examples
are metals, metallic sulphides, sulphur, clay, cotton, paper and silicic aid.
The positively charged colloids in water onsists of a few of the metallic
hydroxides and certain dyes.
The velocity of particles under a fall of potential 1 volt per cm is known as
the electrophoretic mobility. It has been found that the electrophoretic mobility for
aqueous solutions always lies within the range of 2 to 4 × 10–4. It has been frequently
observed that small quantities of electrolytes are necessary for the stability of
colloidal systems. They become unstable if the electrolytes are removed by dialysis.
It appears, therefore, that traces of ions present in the sol are responsible for both
the charge and the stability of the colloidal system. This suggests that the charge is
due to the adsorption of ions from solution, the surface of the particles becoming
covered with a layer of adsorbed ions.
Fig. 12.5 Electrophoretic Apparatus

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The origin of the charge on the colloid is still a matter of some doubt. As a Colloids
first step, particles are hydrated in a sort of complete envelope of water molecules.
NOTES
Fig. 12.6 Origin of the Charge on the Colloidal Particle
The oppositely charged ions present in the solution will be attracted by the
colloidal particle and an electrical double layer is formed as shown in Figure 12.6.
This is similar to the one produced when a metal is in contact with a solution
of its ions. A potential developed between the surface of the particle and the
solution is known as the zeta potential. It is this potential that determines the speed
of the particles. The presence of the electrical double layer renders stability to the
sol particles.
Electro-Osmosis: In the study of electrophoresis, if the colloidal particles are
kept still and only the dispersion medium is allowed to move the phenomenon is
known as electro-osmosis. The apparatus used is shown in Figure 12.7.
Fig. 12.7 Apparatus used for Electro-Osmosis
It consists of a U-tube having its one limb closed with a tap and provided
with a sealed capillary tube C. D is a porous diaphragm which divides the main
compartment into two sections. In each section is placed an electrode as well as
portions of the liquid phase cannot move but the movement of the liquid phase can
be observed as the liquid rises in T. The rate at which the dispersion medium
moves can be measured in terms of the rate of movement of the liquid in capillary
C.
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Material 237
Colloids Precipitation of Colloids by Electrolytes
Numerous terms have been used to denote the process of destroying the colloidal
state and causing the dispersed phase to combine in larger aggregates. Precipitation
is the most general term which implies, ‘to separate from a solution.’ The
NOTES
precipitation of a sol by adding an electrolyte was investigated by Hardy and
Schulze. There are two features of the Hardy-Schulze rule, first the ion which is
effective in causing precipitation of a sol is the one whose charge is of opposite
sign to that of the colloidal particles; the second features states that the precipitating
efficiency increases with the increasing valence of the precipitating ion.
In order to determine the precipitating value of ions, equal volumes of a
certain suspension are precipitated by solutions containing the ions under similar
conditions of concentration and stirring, etc. The precipitation values of some
electrolytes on the same colloidal suspension are given in Table 12.5.
There have been several attempts to arrange ions in a series according to their
precipitating powers but it is found that such a grouping holds only for the
precipitation of a specific sol, and and even then a change in physical conditions
may upset the series. On such series, known as Hofmeister or the lyotropic series,
shows the effect of certain anions of neutral salts upon the precipitation of proteins
and is given below.
SCN– > I– > NO–3 > Br– > Cl– > Acetate > Citrate > Tartrate > SO2– 4.
Sometimes, the precipitation of a colloidal suspension may be done by physical
methods, i.e., stirring, shaking, boiling or freezing the sol.
Table 12.5 Equal volumes of the same sol are used with the
necessary amount of electrolyte to precipitate
Substance in Charge of Electrolyte Millimoles of electrolyte

suspension suspension added for precipitation
As 2 S 3 Negative NaCl 58.0
KCl 50.0
MgSO4 0.81
CaCl2 0.65
AlCl3 0.093
Al(NO2 )3 0.095
Th (NO3)3 0.090
NaCl 9.2
KBr 12.0
BaCl2 9.6
Fe2O2 Positive K2SO4 0.20
MgSO4 0.22
K2Cr2O7 0.19
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12.2.3 The Stabilisation of the Colloidal State Colloids
This process consists in an attempt to neutralise or render ineffective the forces

and conditions by which precipitation can be brought about. For example, if a
stable organic colloid, such as gelatin is added to a metal sol, the latter may be NOTES
prevented from precipitation on the addition of an electrolyte. The addition of a
lyophilic substance to a lyophobic sol usually renders the later less sensitive to the
precipitating effect of electrolytes. The substances that are commonly used as
protective colloid include gelatin, albumin, agar, casein, gum arabic, glue, starch,
etc.
Sols of gold and other metals, dyes, ink, etc., become very stable in presence
of some stabilisers added in small amounts. Zsigmondy introduced the term ‘gold
number’ to measure the protective action of colloids.
The number of milligrams of the protective colloid that just prevents the
change of colour when 1cc of the standard salt solution is added to 10 cc of the
standard gold sol is known as the gold number.
It should be noted from the above definition that the protective colloid having
the least weight, that will prevent the change of colour of the gold sol, has the
greatest protective value. It may be noted that gold number is not a very accurate
constant for a colloid. The reciprocal of gold numbers are used to express the
direct protective ratio. The values of gold numbers and reciprocal gold number for
some substances are given in Table 12.6.
Table 12.6 Gold numbers and reciprocal gold numbers of certain substances
Protective colloid Gold number Reciprocal gold number

Gelatin 0.005 – 0.01 200.0–100.0
Dextrin 6.0 – 20.0 0.17 – 0.05
Gum arabic 0.15 – 0.5 6.7 – 2.0
Albumin 0.1– 0.2 10–5.0
Potato starch 25 0.04
Protective action is a very important phenomenon. It enables colloids to be
kept for a long time when otherwise spontaneous change would take place. Carey
Lea prepared silver sols by reducing silver nitrate with mixtures of ferrous sulphate
and sodium citrate. It contains 99 per cent silver. Such sols are used in medicine
for intravenous injection or as an ointment.
In the preparation of ice cream, little gelatin when added as a protective
colloid gives the cream a smooth paste. Besides gold number, the iron number in
which sols of Fe2O3 are used and the rubin number, which involves sols of congo
red, have also been introduced to measure the protective characteristics of
substances.
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Material 239
Colloids Emulsions
An emulsion is a liquid-liquid suspension, that is small drops of one liquid dispersed
in another liquid. Emulsions are of very common occurrence in nature, the common
examples are milk and mayonnaise. In most emulsions, one of the liquids is water
NOTES
and the other liquid is immiscible with water such as an oil or fat.
When aniline is distilled in steam or an organic liquid, in alcohol or acetone be
poured into excess of water, we get the emulsion ‘oil in water’ type. In this case
we have a few drops of oil dispersed in water. The term ‘oil’ is used to represent
the organic substance insoluble in water. If on the other hand, water is in the form
of droplets dispersed in liquid fat, these emulsions are known as ‘water in oil’
type. The type of emulsion that results on agitation of two liquids depends on the
relative proportion of the two in the mixture. In order to stabilize an emulsion a
third substance known as an emulsifying agent is added. A stable emulsion may be
defined as a substance in which the globules retain their initial character and remain
uniformly distributed throughout the continuous phase. The various deviations from
this ideal behaviour are:
1. Breaking or Cracking: This involves coalescence of the dispersed
globules and produces eventual separation of the emulsion into two phases.
2. Creaming: This involves the concentration of the dispersed globules in
either the upper or lower layers of the emulsion. It is caused by the influence of
gravity on the globules since they usually have a different density from that of the
continuous phase.
3. Coagulation or Flocculation: This involves globules aggregating into loose
masses within the emulsion. The globules do not coalesce and may be redispersed
on shaking. Thus, flocculation is less serious than breaking.
The properties of emulsions are influenced by the effect of impurities and added
substances due to interfacial tension. The emulsifying agent reduces the interfacial
tensioin. The most commonly used emulsifying agents are soap, long chain sulphonic
acids and sulphates which are classified as detergents. The cleansing action of
soap can be ascribed to the formation of an emulsin with oil, grease and water.
Emulsions are usually opaque owing to the difference in refractive index between
the two liquids and the droplets in emulsion are often negatively charged. Emulsions
may be broken into two separate liquid layers by the process known as
demulsification. The conversion of cream into butter by churning is an example of
demulsification.
19.9 Gels
There are some sols that have a high concentration of dispersed solid and change
spontaneously into a semi-solid form known as a gel. For example, gelatin dissolves
in warm water forming a colloidal solution which when cooled sets to a jelly. Gels
are formed by the interlocking of the dispersed particles in the form of a loose
framework inside which liquid dispersion medium is contained. On the basis of
their mechanical properties, gels can be classified into three types.
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 Elastic Gels: They possess the property of elasticity, i.e., their shape is Colloids
altered by applying a small force and is restored to the original shape

when the force is removed. The examples of elastic gels are starch, gelatin,
fruit jam and jellies. The molecules are held up by electrostatic forces
between the ionized or polar groups. NOTES
 Rigid Gels: The best known example of this type is that of silicic acid,
known as silica gel. A network of chemical bonds gives them a rigid
structure.
 Thixotropic Gels: Such gels become semi-solid when at rest but become
liquid when vigorously agitated. Kieselguhr and water form a thin paste
when tilted slowly. The mixture does not flow but flows readily on
shaking solutions of some high polymers exhibit these properties. These
are held up by weak attractive forces.
The term gel represents a physical state with properties intermediate between
those of solids and liquids. The gels should satisfy the following criteria:
 They are coherent colloidal systems of at least two components (the gelling
agent and a fluid component).
 They exhibit mechanical properties characteristic of the solid state.
 Each component is continuous throughout the system.
These criteria are fulfilled by gelatin, agar and bentonite gels in which the
fluid component is aqueous and by soft paraffin in which the fluid component is
an organic liquid.
Many gels shrink if the fluid component is removed for example, by evaporation
or freeze-drying. The remaining solid which will swell and reform the gel on contact
with fresh foluid component is termed a xerogel. Gelatin sheets, acacia tears, starch
grain and leather are all xerogels.
The Structure of Gels

The rigidity of a gel arises from the presence of a network formed by the interlinking
of particles of the gelling agent. The nature of the particles and the type of force
that is responsible for the linkages determines the structure of the network and
the properties of the gel.
The individual particles of a hydrophilic colloid may consist of either spherical
or anisometric aggregates of small molecules or single macromolecules. The forces
of attraction responsible for the linkages between gelling agent particles may range
from strong primary valencies, as in silicic acid gels, to weaker hydrogen bonds
and van der Waals forces. The weaker nature of these latter forces is indicated by
the fact that a slight increase in temperature often causes liquefaction of a gel.
Systems that exhibit this type transition such as agar and gelatin gels are termed as
thermal gels. In addition the transition from gel state to a colloidal dispersion may
in some cases be brought about by mechanical agitation. They systems exhibiting
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Material 241
Colloids such type of transition are called thixotropic gels. The common exampels are
bentonite and aluminium hydroxide gels.
Properties of Gels
NOTES  Swelling: If a xerogel is placed in contact with a liquid that solvates it,
then an appreciable amount of the liquid is often taken up and the volume
of xerogel increases. This is called swelling. The degree of swelling depends
on the number of linkages between individual molecules of gelling agent
and on the strength of these linkages. For example in a protein xerogel,
swelling is at a minimum at the iso-electric point of the protein because the
intermolecular linkages are strongest at this point and, therefore, offer more
resistance to swelling. The presence of ions influence the degree of swelling.
 Syneresis: Gel will often contract spontaneously and exude some of the
fluid medium. This effect is known as syneresis and the degree to which it
occurs usually decreases as the concentration of the gelling agent increases.
Blood clot is a common example of a system that exhibits syneresis.
 Ageing: Colloidal systems usually exhibit slow spontaneous aggregation.
This is referred to as ageing. In gels, ageing results in the gradual formation
of a denser network of gelling agent.
 Rheological properties: Gels exhibit the mechanical properties of rigidity,
tensile strength, and elasticity that are characteristic of solids. In thixotropic
gels, these effects are only apparent below the yield value, above which
the system exhibits the flow properties of suspensions.
Application of Gels
Gelatin gels are employed in the preparation of hard and soft capsules that may be
used to mask the unpleasant tastes of solids and liquid. Agar and gelatin gels are
used as solid media for the culture of micro-organisms. The diffusion of antibiotics,
antiseptics, vitamins and enzymes through solid culture media is used in
microbiological assay of these materials.
There are a number of important processes in which colloids play an important
role.
 A very useful application is in Cottrell precipitation, as purification process
for industrial smoke. The air near the factories and industrial plants is frequently
contaminated with smoke and gases which result from the manufacturing
processes. The smoke is laden with colloidal particles, such as cement dust,
arsenic compounds and metallic powder, which are irritating and even
poisonous. The Cottrell precipitator (Refer figure 12.8) removes colloidal
particles from the flue gases by means of electrical precipitation. In the
Cottrell precipitator, flue gases are passed over wires maintained at high
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voltage where suspended particles acquire an electric charge. A collecting Colloids
plate of opposite charge attracts the charged particles which loose their
charge and fall to the bottom. The air pollution is thus reduced to a minimum.
 Leather tannin is a process which utilises colloidal properties. Raw hides
NOTES
contain giant molecules arranged in long tangled fibres. Tanning materials
which include tannin and compounds of chromium and aluminium are in
colloidal state and the positively charged protein fibres adsorb negative
charges from these metallic ingredients.
 In textile dyeing, colloidal substances called mordants are used to fasten
dyes.
 In purification of water, aluminium sulphate and lime are added to form a
flocculant precipitate of aluminium hydroxide. This precipitate will adsorb
very fine particles of clay or other suspended matter and carry them to the
seetting tanks or basins. The reaction can be symbolized as
Al2 (SO4)3 + 3Ca(OH)2 = 2Al (OH)3  + 3CaSO4
 Formation of deltas: Extensive deposits of silt or clay formed at the mouths
of rivers by colloidal action are called deltas.
Fig. 12.8 Cottrell precipitator
 The cleansing action of detergents is due to former’s emulsifying properties.

They form an emulsion with oil and dirt particles in water.
 Sewage usually contains considerable amounts of deflocculating substances
such as soap, organic matter and the like which tend to keep it full of
colloidally dispersed particles. The successful treatment of sewage,
backwaters and trade effluents involves the separation from them these
colloids by coagulation, absorption, filtration or destruction (usually by
bacteria in the septic tank).
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Colloids  Smoke screens consist of titanium dioxide particles dispersed in air and are
used in warfare for the purpose of concealment.
 ‘Fire-foam’ is a carbon dioxide froth made by mixing solution of sodium
bicarbonate and alum. A protective colloid such as glue, dextrin or saponin
NOTES
is added to stabilize the foam and keep the bubbles in finely dispersed
form.
 Colloids are of great importance in living systems, for protoplasm itself is a
gel. It contains considerable amount of protein, glycogen and phospholipid;
all are lyophilic materials. Molecules of these substances exhibit inhebition
that is they attract water strongly and so firmly that the water is said to be
bound. This water cannot even freeze. When the particles in colloids
rearrange and force some of the bound water out, syneresis is said to occur.
In the digestive track, bile salts serve as agents to convert temporary aqueous
oil emulsions to more permanent ones. It has been suggested that the efficiency
of certain substances used in pharmaceutical preparations may be increased
if colloidal forms are used, since these have large surface areas; for example
the adsorption of toxins from the gastro intestinal tract by kaolin and the
rate of neutralisation of excess acidity in stomach by aluminium hydroxide
may be increased if these compounds are used in colloidal forms.
The use of colloidal iron and colloidal iodine is said to alter the effect of
these compounds.
Blood plasma substitutes are colloidal dispersions in which the particle size
in such that they are retained in the blood vessels for an adequate time. Colloidal
gold, calcium and silver are used in medicines or as ointment.
Check Your Progress

1. What are colloids ?
2. What are hydrophilic and hydrophobic colloids ?
3. Give a difference between reversible and irreversible system .
4. What is a dispersed phase and dispersion medium?
5. What system of classification of colloids can be employed when the
dispersion medium is liquid ?

QUESTIONS
1. Colloids are a mixture of two substances, in which one substance is divided
into minute particles aka colloidal particles (ranging from 1 to 1000 nm in
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diameter) and dispersed or suspended over another substance. These Colloids
insoluble particles are inseparable either by filtering or centrifuging. Types

of Colloids are Sol, Emulsion, Foam, and Aerosol.
2. Hydrophilic colloids are water-loving colloids. The colloid particles are
attracted toward the water. They are also known as reversible sols. NOTES
Examples include Agar, gelatin, pectin, etc. While hydrophobic colloids are
opposite in nature to hydrophilic colloids. The colloid particles are repelled
by water. They are also called irreversible sols. Examples include Gold
sols, clay particles, etc.
3. In a reversible system the products of a physical or chemical reaction may
be induced to interact so as to reproduce the original components while in
an irreversible system is one in which the products of a reaction are so
stable or are removed so effectively from the system that its original
components cannot be reproduced.
4. The substances which are dispersed in the solution are called dispersed
phase and the solution in which it is dispersed is called dispersion medium.
5. Depending upon the state of dispersed particles and the dispersion medium,
the following system of classification of colloids can be employed when the
dispersion medium is liquid:
 Foams: When the dispersed medium is gas. Examples include whipped
cream, shaving cream, etc.
 Emulsions: When the dispersed phase is liquid. Examples include
milk, mayonnaise, etc.
 Sol: When the dispersed phase is solid. Examples include blood,
pigmented ink, etc.
12.4 SUMMARY
 Colloids, in chemistry, are a mixture of two substances, in which one

substance is divided into minute particles aka colloidal particles (ranging
from 1 to 1000 nm in diameter) and dispersed or suspended over another
substance.
 A colloid is a mixture in which one substance of microscopically dispersed
insoluble particles are suspended throughout another substance. Sometimes
the dispersed substance alone is called the colloid.
 The colloid consists of a dispersed phase and a continuous phase. Unlike
solutions, colloids do not constitute a solute dissolved in the solvent phase.
Rather, the solute phase is dispersed in the solvent phase.
 Colloids are generally classified into two systems, reversible and irreversible.
In a reversible system the products of a physical or chemical reaction may
be induced to interact so as to reproduce the original components.
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Colloids  An irreversible system is one in which the products of a reaction are so
stable or are removed so effectively from the system that its original
components cannot be reproduced. Examples of irreversible systems include
sols (dilute suspensions), pastes (concentrated suspensions), emulsions,
NOTES foams, and certain varieties of gels. The size of the particles of these colloids
is greatly dependent on the method of preparation employed.
 A colloid is a mixture in which one substance which has fine particles
(dispersed phase) mixed into another substance (dispersion medium). The
particles of the colloids have a range from 1 to 1000 nm in diameter. The
solution is called colloidal dispersion because the particles of solutions do
not mix or settle down. They are dispersed in the solution.
 The substances which are dispersed in the solution are called dispersed
phase, and the solution in which it is dispersed is called dispersion medium.
 A colloidal system in which the dispersion medium is a liquid or gas is called
sols. They are called hydrosols or aqual sols. If the dispersion medium is
water. When the dispersion medium is alcohol or benzene, they are
accordingly called alcohols or benzosol.
 Colloidal systems in which the dispersion medium is air are called aerosols.
 Colloids in which the dispersion medium is a solid are called gels, for
example, cheese etc. They have a more rigid structure. Some colloids, such
as gelatin, can behave both as a sol and a gel.
 At high temperature and low concentration of gelatin, the colloids is
hydrosol. But at low temperature and high gelatin concentration, the hydrosol
can change into a gel.
 In macromolecular colloids the macromolecules form a solution with a
suitable solvent. The size of the particles of this macromolecular solution
lies in the range of colloidal particles size. Thus this solution is also known
as the macromolecular colloids. The colloids formed here are similar to that
of the actual solution in many respects and are very stable.
 In associated colloids some substances act as a strong electrolyte when
they are in low concentrations, but they react as colloidal sols when they
are in high concentration. In higher concentration, particles aggregate showing
a colloidal behavior. These aggregated particles are known as the micelles.
 These colloids can be reverted by diluting it. Examples of some associated
colloids are soaps and synthetic detergents.
 If the dispersed phase has an affinity for the dispersion medium, the colloid
is called a lyophilic colloid. The words lyo and philic means ‘liquid’ and
‘loving’ respectively. Thus, even if the dispersed phase is separated from
the dispersion medium, they can readily be reconstituted by simply mixing
them.
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Colloids
12.5 KEY WORDS
 Hydrophilic colloids: These are water-loving colloids. The colloid particles

are attracted toward the water. They are also known as reversible sols. NOTES
Examples include Agar, gelatin, pectin, etc.
 Hydrophobic colloids: These are opposite in nature to hydrophilic colloids.
The colloid particles are repelled by water. They are also called irreversible
sols. Examples include Gold sols, clay particles, etc.
 Reversible system: In a reversible system the products of a physical
or chemical reaction may be induced to interact so as to reproduce the
original components.
 Irreversible system: An irreversible system is one in which the products
of a reaction are so stable or are removed so effectively from the system
that its original components cannot be reproduced.
 Dispersed phase: The substances which are dispersed in the solution are
called dispersed phase.
 Dispersion medium: The solution in which it is dispersed is called dispersion
medium.

EXERCISES

1. Write a short note on colloids.
2. What is dispersed phase and dispersion medium ?
3. Name the types of colloids.
4. Give some examples of colloids.
5. Depending upon the state of dispersed and dispersion medium what system
of classification of colloids can be employed ?
6. What are optical properties of colloids ?
7. Give any two applications of colloids.
1. Write a elaborated note on colloids explaining its types and examples.
2. Distinguish between lyophilic sols and lyophobic solutions.
3. Give a table to show the types of colloidal dispersions.
4. Give the major characteristics of lyophilic and lyophobic solutions.
5. Elaborate on the properties of colloids.
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Colloids 6. Explain the stabilisation of colloidal state.
7. How are colloids prepared? Discuss in detail.
8. Explain the precipitation of colloids by electrolytes.
NOTES 9. Write in detail about emulsions and gels.
10. List the major applications of colloids.

& Company Ltd.
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Solar Energy
UNIT 13 SOLAR ENERGY Conversion: Polymers

and Polymerization
CONVERSION: POLYMERS
NOTES
AND POLYMERIZATION
Structure
13.0 Introduction
13.1 Objectives
13.2 Solar Energy Conversion: Polymers Basics
13.3 Conducting Polymers
13.4 Polymer Electrolyte and Fire Retardant Polymer
13.4.1 Fire Retardant Polymer
13.5 Thermally Stable and Biodegradable Polymers
13.6 Atom Radical Polymerization: Basic Mechanism and Applications
13.6.1 Dendrimer
13.8 Summary
13.9 Key Words
13.0 INTRODUCTION
Polymers are defined as any of a class of natural or synthetic substances composed

of very large molecules, called macromolecules that are multiples of simpler chemical
units called monomers.
The term ‘Polymer’ is derived from the Greek word ‘Polus’ meaning ‘many,
much’ and ‘Meros’ meaning ‘part’. Principally it refers to a molecule whose structure
is composed of multiple repeating units, from which originates a characteristic of
high relative molecular mass and attendant properties. The units composing polymers
are typically derived, actually or conceptually, from molecules having low relative
molecular mass. A molecule of high relative molecular mass, the structure of which
essentially comprises the multiple repetition of units derived, actually or conceptually,
from molecules of low relative molecular mass.
Conductive polymers or more precisely Intrinsically Conducting Polymers
(ICPs) are specific organic polymers that conduct electricity. Such compounds
may have metallic conductivity or can be semiconductors. The principal advantage
of conductive polymers is their process ability, mainly by dispersion. Conductive
polymers are generally not thermoplastics, i.e., they are not thermoformable. But,
like insulating polymers, they are organic materials.
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Solar Energy In this unit, you will study about solar energy conversion, polymers basics,
Conversion: Polymers
and Polymerization conducting polymers, polymer electrolyte and fire retardant polymer,
thermally stable and biodegradable polymers, atom radical polymerization and its
basic mechanism and applications in detail.
NOTES
13.1 OBJECTIVES

 Understand the concept of solar energy conversion
 Discuss the polymers basics and conducting polymers
 Explain about polymer electrolyte and fire retardant polymer
 Understand about thermally stable and biodegradable polymer
 Discuss about atom radical polymerization and its basic mechanism
and applications
13.2 SOLAR ENERGY CONVERSION: POLYMERS

BASICS
The term ‘Polymer’ is derived from the Greek word ‘Polus’ meaning ‘many,
much’ and ‘Meros’ meaning ‘part’. Principally it refers to a molecule whose structure
is composed of multiple repeating units, from which originates a characteristic of
high relative molecular mass and attendant properties. The units composing polymers
are typically derived, actually or conceptually, from molecules having low relative
molecular mass.
Both the synthetic and the natural polymers essentially have diverse roles in
our day-to-day life, because of their extensive properties. Polymers range from
familiar synthetic plastics, such as polystyrene to natural biopolymers, such as
DNA (Deoxyribo Nucleic Acid) and proteins that are fundamental units to biological
structure and function. Polymers, both natural and synthetic, are created via
polymerization of many small molecules, termed as ‘monomers’. The consequently
large molecular mass of polymers relative to their small molecule compounds
produces exceptional physical properties, including toughness, viscoelasticity, and
a tendency to form glasses and semi-crystalline structures. The terms polymer and
resin are often synonymous with plastic.
Definition: A polymer is a large molecule or a macromolecule composed of many
repeated subunits.
Definition: Polymers are defined as any of a class of natural or synthetic substances
composed of very large molecules, called macromolecules that are multiples of
simpler chemical units called monomers.
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The term ‘Polymer’ was coined in 1833 by Jöns Jacob Berzelius, though with a Solar Energy
definition distinct from the modern IUPAC definition. The modern concept of and Polymerization
polymers as covalently bonded macromolecular structures was proposed in 1920
by Hermann Staudinger, who spent the next decade finding experimental evidence
for this hypothesis. NOTES
IUPAC Definitions of Polymer and Macromolecule
Polymer: Polymer is a substance composed of macromolecules also termed as
polymer molecules.
Macromolecule: A molecule of high relative molecular mass, the structure of
which essentially comprises the multiple repetition of units derived, actually or
conceptually, from molecules of low relative molecular mass.
Polymers are specifically defined on the basis of biophysics and
macromolecular science, and polymer science (which includes polymer chemistry
and polymer physics). Historically, the structure of polymer products were defined
having the linkage of repeating units by covalent chemical bonds now defined on
the theory of non-covalent links. Polyisoprene of latex rubber is an example of a
natural/biological polymer, while the polystyrene of styrofoam is an example of a
synthetic polymer. In biology, essentially all biological macromolecules, i.e., proteins
(polyamides), nucleic acids (polynucleotides), and polysaccharides are purely
polymeric or are defined as compounds which are composed in large part of
polymeric components, for example isoprenylated/lipid-modified glycoproteins,
where small lipidic molecules and oligosaccharide modifications occur on the
polyamide backbone of the protein.
Polymers, thus, constitute the different materials in living organisms, such as
proteins, cellulose, and nucleic acids. Moreover, they also constitute the basis of
minerals, such as diamond, quartz, and feldspar and man-made materials, such as
concrete, glass, paper, plastics, and rubbers. The simplest theoretical models for
polymers are ideal chains. Figure 13.1 illustrates the appearance of real linear
polymer chains as recorded using an atomic force microscope on a surface, under
liquid medium. Chain contour length for this polymer is recorded as ~204 nm and
the thickness as ~0.4 nm.
Fig. 13.1 Real Linear Polymer Chains (Courtesy: Wikipedia) Self-Instructional

Material 251
Solar Energy Polymers are of two types, naturally occurring polymers and synthetic or man-
and Polymerization made polymers.
Natural polymers include hemp, shellac, amber, wool, silk and natural rubber.
In addition, the natural polymer cellulose is the main constituent of wood and
NOTES
paper.
Synthetic polymers include polyethylene, polypropylene, polystyrene,
polyvinyl chloride, synthetic rubber, phenol formaldehyde resin (or Bakelite),
neoprene, nylon, polyacrylonitrile, PVB, silicone, and many more. Million tons of
these polymers are made every year.
Structure of Polymers
The various common classes of polymers are composed of hydrocarbons, the
compounds of carbon and hydrogen. These polymers are precisely made of carbon
atoms that are bonded together, one to the next, into long chains termed as the
linked backbone of the polymer. The carbon allows other atoms (single or more)
to be attached to each carbon atom in the polymer chain. There are polymers that
contain only carbon and hydrogen atoms, such as polyethylene, polypropylene,
polybutylene, polystyrene and polymethylpentene. In the PolyVinyl Chloride (PVC),
the chlorine is attached to the all the carbon in the polymer chain while in Teflon the
fluorine is attached to the all the carbon in the polymer chain. In some of the
polymer backbones or the polymer chain, the Oxygen is also present, such as
polyethylene glycol, polysaccharides (in glycosidic bonds), and DNA (in
phosphodiester bonds).
Standardized Nomenclature: Polymers
There are multiple conventions for naming polymer substances. Many commonly
used polymers are referred to by a common or trivial name. The trivial name is
assigned based on historical precedent or popular usage rather than a standardized
naming convention. Both the American Chemical Society (ACS) and International
Union of Pure and Applied Chemistry (IUPAC) have proposed standardized naming
conventions. Though both the ACS and IUPAC conventions are similar but not
identical. Table 13.1 shows the difference between the various naming conventions.
Table 13.1 Different Naming Conventions
Common Name ACS Name IUPAC Name
Poly(ethylene
Poly(oxyethylene) Poly(oxyethene)
oxide) or PEO
Poly(ethylene Poly(oxy-1,2-
terephthalate) or ethanediyloxycarbonyl- Poly(oxyetheneoxyterephthaloyl)
PET 1,4-phenylenecarbonyl)
Poly[amino(1-oxo-1,6- Poly[amino(1-oxohexan-1,6-
Nylon 6
hexanediyl)] diyl)]
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In both standardized conventions, the name of the polymers specifies or reflects Solar Energy
the monomer(s) from which they are synthesized rather than the precise nature of and Polymerization
the repeating subunit. For example, the polymer synthesized from the simple alkene
‘Ethene’ is termed as ‘Polyethylene’ which retains the ‘-ene’ suffix even though
the double bond is removed during the polymerisation process as shown below in NOTES
Figure 13.2.
Fig. 13.2 Polymerisation of Ethene into Poly(Ethene)
Synthesis of Polymers
Polymer synthesis, also called polymerization, is the process by which monomers
(small molecules) are covalently bonded to form a usually long chain of polymer.
Polymerization is, thus, the process of combining many small molecules
termed as monomers into a covalently bonded chain or network. During the
polymerization process, some chemical groups may be lost from each monomer.
This situation occurs in the polymerization of PET polyester. The monomers are
terephthalic acid (HOOC—C6H4—COOH) and ethylene glycol (HO—CH2—
CH2—OH) but the repeating unit is —OC—C6H4—COO—CH2—CH2—O—
, which corresponds to the combination of the two monomers with the loss of two
water molecules. The distinct or individual piece of each monomer that is
incorporated into the polymer is termed as a repeat unit or monomer residue.
Figure 13.3 illustrates the repeating unit of the polymer polypropylene.
Fig. 13.3 Repeating Unit of the Polymer Polypropylene
Laboratory synthetic methods are generally divided into following two categories:
1. Step Growth Polymerization
2. Chain Growth Polymerization
The essential difference between the two is that in chain growth polymerization,
monomers are added to the chain one at a time only, such as in polyethylene,
whereas in step growth polymerization chains of monomers may combine with
one another directly, such as in polyester. However, the plasma polymerization is
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Solar Energy the exception which do not fit neatly into either of the above defined categories.
and Polymerization Synthetic polymerization reactions may be carried out with or without a catalyst.
Polymer Characterization Techniques
NOTES Polymer characterization includes several techniques for determining the chemical
composition, molecular weight distribution, and physical properties. Following are
some common selected techniques that are widely used:
 Size-Exclusion Chromatography: The size-exclusion chromatography
is also termed as gel permeation chromatography. It is sometimes coupled
with static light scattering and can be used to determine the number-average
molecular weight, weight-average molecular weight, and dispersity.
 Scattering Techniques: The scattering techniques, such as static light
scattering and small-angle neutron scattering are typically used to determine
the dimensions (radius of gyration) of macromolecules in solution or in the
melted state. These techniques are also used to characterize the three-
dimensional structure of microphase-separated block polymers, polymeric
micelles, and other materials.
 Wide-Angle X-Ray Scattering: The wide-angle X-ray scattering is also
termed as wide-angle X-ray diffraction. It is used to determine the crystalline
structure of polymers (or lack thereof).
 Spectroscopy Techniques: The spectroscopy techniques including
Fourier-transform infrared spectroscopy, Raman spectroscopy, and nuclear
magnetic resonance spectroscopy, are specifically used to determine the
chemical composition.
 Differential Scanning Calorimetry: The differential scanning calorimetry
technique is used to characterize the thermal properties of polymers, such
as the glass transition temperature, crystallization temperature, and melting
temperature. The glass transition temperature can also be determined by
dynamic mechanical analysis.
 Thermogravimetry: The thermogravimetry is a significant technique used
to evaluate the thermal stability of the polymer.
 Rheology: The rheology technique is used to characterize the flow and
deformation behaviour. It can be used to determine the viscosity, modulus,
and other rheological properties. Rheology is also often used to determine
the molecular architecture (molecular weight, molecular weight distribution,
branching) and to understand how the polymer can be processed.
Characteristic Features/Properties of Polymers
Most of the manufactured polymers are thermoplastic, meaning that once the
polymer is formed it can be heated and reformed over and over again. This property
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allows for easy processing of polymers and also facilitates polymer recycling. The Solar Energy
polymers which are thermosets cannot be re-melted or recycled. Once these and Polymerization
polymers are formed, reheating will cause the material to ultimately degrade, but
not melt.
NOTES
Every polymer has very distinct characteristics, but most polymers have the
following general attributes.
 Polymers can be very resistant to chemicals.
 Polymers can be both thermal and electrical insulators.
 Polymers are usually very light in weight with significant degrees of strength.
 Polymers can be processed in various ways.
 Polymers are materials with a seemingly limitless range of characteristics
and colours.
 Polymers are usually made of petroleum, but not always.
 Polymers can be used to make items that have no alternatives from other
materials.
Applications of Polymers
Polymers have a range of applications as compared to any other class of material
available to man. Current applications extend from adhesives, coatings, foams,
and packaging materials to textile and industrial fibers, composites, electronic
devices, biomedical devices, optical devices, and precursors for many newly
developed high-tech ceramics. Following are some common applications of
polymers:
Agriculture and Agribusiness: Polymeric materials are used in and on soil to
improve aeration, provide mulch, and promote plant growth and health.
Medicine: Many biomaterials, especially heart valve replacements and blood
vessels, are made of polymers like Dacron, Teflon and Polyurethane.
Consumer Science: Plastic containers of all shapes and sizes are light weight and
economically less expensive than the more traditional containers. Clothing, floor
coverings, garbage disposal bags, and packaging are other polymer applications.
Industry: Automobile parts, windshields for fighter planes, pipes, tanks, packing
materials, insulation, wood substitutes, adhesives, matrix for composites, and
elastomers are all polymer applications used in the industrial market.
Sports: Playground equipment, various balls, golf clubs, swimming pools, and
protective helmets are often produced from polymers.
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Solar Energy
and Polymerization Check Your Progress
1. Define polymer.
NOTES 2. Who coined the term polymer and when?
3. What is a macromolecule?
4. How many types of polymers are there?
13.3 CONDUCTING POLYMERS
They can provide high electrical conductivity but do not show similar mechanical
properties to other commercially available polymers. The electrical properties can
be perfectly adjusted using the methods of organic synthesis and by advanced
dispersion techniques.
Polyaniline was first described in the mid-19th century by Henry Letheby, who
investigated the electrochemical and chemical oxidation products of aniline in acidic
media. He noted that reduced form was colourless but the oxidized forms were of
deep blue colour.
The first highly-conductive organic compounds were the charge transfer complexes.
There are evidences that the polycyclic aromatic compounds formed semi-
conducting charge-transfer complex salts with halogens. Organic Light-Emitting
Diodes (OLEDs) are the significant application of conducting polymers.
Figure 13.4 illustrates the chemical structures of some conductive polymers. Starting
from top left they are clockwise named as Polyacetylene, Polyphenylene Vinylene,
Polypyrrole (X = NH) and Polythiophene (X = S), and Polypyrrole (X = NH)
and Polyphenylene Sulfide (X = S).
Fig. 13.4 Chemical Structures of Some Conductive Polymers
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Types of Conductive Polymers Solar Energy
and Polymerization
Linear backbone ‘Polymer Blacks’ typically includes polyacetylene, polypyrrole,
polyindole and polyaniline, and their copolymers which form the main class of
conductive polymers. Poly(P-Phenylene Vinylene) or PPV and its soluble NOTES
derivatives have been developed as the prototypical electroluminescent
semiconducting polymers. These days, poly(3-alkylthiophenes) are considered
as the archetypical materials for solar cells and transistors.
Table 13.2 shows some organic conductive polymers according to their
composition.
Table 13.2 Some Organic Conductive Polymers
Heteroatoms Present
Main
Chain
Nitrogen-
Contains No Heteroatom Sulfur-Containing
Containing
The N is in the
Aromatic Cycle: The S is in the Aromatic
Cycle:
 Poly(Pyrrole)s
 Poly(Fluorene)s (PPY)  Poly(Thiophene)s (PT
)
 Polyphenylenes  Polycarbazoles
 Poly(3,4-
Aromatic  Polypyrenes  Polyindoles
Ethylenedioxythiophe
Cycles Polyazulenes Polyazepines
  ne) (PEDOT)
 Polynaphthalen The N is Outside The S is outside the
es the Aromatic Aromatic Cycle:
Cycle:
 Poly(P-Phenylene
 Polyanilines Sulfide) (PPS)
(PANI)
Double  Poly(Acetylene
Bonds )s (PAC)
Aromatic
 Poly(P-
Cycles
Phenylene
and
Vinylene) (PP
Double
V)
Bonds
Synthesis of Conductive Polymers

Conductive polymers are prepared using various methods. Most of the conductive
polymers are prepared by oxidative coupling of monocyclic precursors. Such
reactions entail dehydrogenation as shown below:
The low solubility of most polymers show unique behaviour. At times the
solubilizing functional groups are added to some or all monomers to increase
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Solar Energy solubility. Some conductive polymers exhibit the formation of nanostructures and
and Polymerization surfactant-stabilized conducting polymer dispersions in water, such as polyaniline
nanofibers. In numerous situations, the molecular weight of conductive polymers
are lower than conventional polymers, such as polyethylene. However, in some
NOTES situations the molecular weight must not be high in order to achieve the desired
properties.
There are two main methods used in the synthesis of conductive polymers,
namely the chemical synthesis method and the electro (co)polymerization method.
The chemical synthesis defines the connecting carbon-carbon bond of monomers
by placing the simple monomers under various conditions, such as heating, pressing,
light exposure and catalyst. The advantage is high yield. However, there are many
impurities plausible in the end product. The electro (co)polymerization specifies
that the three electrodes (reference electrode, counter electrode and working
electrode) are inserted into solution including reactors or monomers. When the
voltage is applied to electrodes then the redox reaction takes place to synthesize
polymer. Electro (co)polymerization method can also be divided into ‘Cyclic
Voltammetry’ and ‘Potentiostatic’ methods in which the cyclic voltage and constant
voltage are applied. The advantage of electro (co)polymerization method is that it
ensures high purity of products. But this method can only synthesize a few products
at a time.
Applications of Conductive Polymers
Following are some applications of conductive polymers:
 Provide electromagnetic shielding of electronic circuits.
 Used as antistatic coating material to prevent electrical discharge exposure
on photographic emulsions.
 Used as hole injecting electrodes for OLEDs (Organic Light Emitting
Devices).
 Used in electroluminescent displays (mobile telephones).
 Used as emissive layer in full-colour video matrix displays.
 Capable for FETs (Field-Effect Transistors).
 Capable of absorbing microwaves, the stealth technique.
Check Your Progress

5. How are conducting molecules prepared?
6. How is synthesis of conductive polymers carried out?
7. Give some applications of conductive polymers.
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Solar Energy
13.4 POLYMER ELECTROLYTE AND Conversion: Polymers
and Polymerization
FIRE RETARDANT POLYMER
Polymer electrolytes or gel-type polymer electrolytes are the alternatives to NOTES

substitute liquid electrolytes in Dye-Sensitized Solar Cells (DSSCs). A polymer
electrolyte is also referred to as a solid solvent that possesses ion transport
properties similar to that of the common liquid ionic solution. It usually comprises
a polymer matrix and electrolyte, wherein the electrolyte, such as a lithium salt
dissolves in a polymer matrix. The polymer electrolytes are complexes of alkali
metal salts (MX), with polymers as the host matrix.
Properties of Polymer Electrolyte
Following are the properties of polymer electrolyte:
 Adequate conductivity for practical purposes
 Low electronic conductivity
 Good mechanical properties
 High chemical, electrochemical and photochemical stability
 Ease of processing
Fundamentals of Polymer Electrolyte
Following are the fundamental types of polymer electrolyte:
1. Solvent (Liquid) Free System: This ionically conducting phase is formed
by dissolving salts in polymer.
2. Gel Electrolyte: This is formed by dissolving salt in polar liquid and adding
inactive polymeric material.
3. Plasticized Electrolyte: This is fundamentally a gel electrolyte but is
typically associated with the addition of small amounts of a high dielectric
constant solvent which enhances its conductivity.
4. Ionic Rubber: The ionic rubber is a liquid electrolyte which comprises of a
low temperature molten salt mixture and then reduced to a rubbery condition
by addition of a small amount of high Mw polymer.
Electrically Conducting Solution of a Salt in a Polymer Electrolyte
The most common example of a solid polymer electrolyte is a solution of a lithium
salt in a poly(oxyethylene) matrix. The ionic conductivity is because of the mobility
of lithium cations and their counter ions in an electric field. Both the terms solid
polymer electrolyte and polymeric electrolyte are different and one should not be
confused with the terms.
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Solar Energy 13.4.1 Fire Retardant Polymer
and Polymerization
Fire safe polymers are particular type of polymers that are resistant to degradation
at high temperatures. The fire resistant polymers are essentially required in the
NOTES construction of small, enclosed spaces, such as skyscrapers, boats, and airplane
cabins. In these tight spaces, ability to escape in the event of a fire is compromised,
increasing fire risk. Fire safe polymers also have application as adhesives in
aerospace materials, insulation for electronics, and in military materials, such as
canvas tenting.
Some of the fire safe polymers naturally exhibit an intrinsic resistance to
decomposition, while the other polymers are typically synthesized by incorporating
fire resistant additives and fillers. Standard methods for testing polymer flammability
is diverse in different countries.
Polymer Combustion
Traditional polymers decompose under heat and produce combustible products,
thus, they are able to originate and easily propagate fire, as shown in Figure 13.5.
Fig. 13.5 General Scheme of Polymer Combustion
The process of combustion initiates when heating a polymer yields volatile products.
If these products are sufficiently concentrated within the flammability limits and at
a temperature above the ignition temperature, then combustion process continues.
As long as the heat supplied to the polymer remains sufficient to sustain its thermal
decomposition at a rate exceeding that required to feed the flame, combustion will
continue.
Purpose and Methods of Fire-Retardant Systems
The purpose is to control heat below the critical level. To achieve this, an
endothermic environment is created for producing non-combustible products, or
the chemicals are added that would remove fire propagating radicals, such as H
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260 Material
and OH, etc. These specific chemicals can be added into the polymer molecules Solar Energy
either permanently or as additives and fillers. and Polymerization
Role of Oxygen: Oxygen catalyzes the pyrolysis of polymers at low concentration
and initiates oxidation at high concentration. Transition concentrations are different
NOTES
for different polymers, for example polypropylene, between 5% and 15%. In
addition, polymers exhibit a structural-dependent relationship with oxygen. Some
structures are intrinsically more sensitive to decomposition upon reaction with
oxygen. The amount of access that oxygen has to the surface of the polymer also
plays a role in polymer combustion. Oxygen is capable to interact with the polymer
before a flame has actually been ignited.
Role of Heating Rate: In most of the situations, results from a typical heating
rate do not differ significantly from those obtained at higher heating rates, for
example 10™/min for mechanical thermal degradation analysis. The extent of
reaction can, however, be influenced by the heating rate. For example, some
reactions may not occur with a low heating rate due to evaporation of the products.
Role of Pressure: Volatile products are removed more efficiently under low
pressure, which means the stability of the polymer might have been compromised.
Decreased pressure also slows down decomposition of high boiling products.
Check Your Progress

8. List the properties of polymer electrolyte.
9. How is gel electrolyte formed?
10. What is plasticized electrolyte?
13.5 THERMALLY STABLE AND

BIODEGRADABLE POLYMERS
Polymers are found everywhere on the earth. Most of the polymers that are used
on an everyday basis are obtained from petroleum-based products.
Most organic polymeric materials melt below 200°C and most of them
begin to degrade rapidly at temperatures only slightly above 200°C. Thermally
stable polymers are generally considered to be those which will withstand much
higher temperatures without loss of strength or change of structure. In general the
thermally stable materials are those which withstand at least 300°C in air and up
to 500°C or higher in inert atmospheres. Polymers which show these properties
are usually highly aromatic in structure, often with heterocyclic units, high melting,
sometimes infusible and usually with low solubility in all solvents. This makes their
fabrication very difficult and as a consequence they are of limited use.
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Solar Energy There are a relatively few polymers which are commercially available as
and Polymerization plastics, films, wire-coating polymers, etc., which are stable in the indicated
temperature ranges.
Biodegradable Polymer
NOTES
The biodegradable polymer are those polymers which can decompose under
aerobic or anaerobic conditions because of the action of microorganism/enzymes.
The materials develop it like starch, cellulose, and polyesters. Aliphatic polyesters
are the most commonly used polymers of this type. Following are some common
examples of biodegradable polymers:
Poly β-Hydroxybutyrate – Co-β-Hydroxy Valerate (PHBV): It
is derived by combining 3-hydroxy butanoic acid and 3-hydroxy pentanoic acid,
in which monomers are cross-linked by an ester linkage. It decomposes to form
carbon dioxide and water. It is brittle in nature, and it can be used in the production
of drugs and manufacturing of bottles.
Nylon 2–Nylon 6: It is a polyamide copolymerisation of glycine (H2N–CH2–
COOH) and aminocaproic acid (H2N–(CH2)5–COOH).
Polyhydroxy Butyrate (PHB): It is formed by the condensation of hydroxybutyric
acid (3-hydroxy butanoic acid) molecules.
Structure of Biodegradable Polymers
Biodegradable polymers tend to consist of ester, amide or ether bonds. In general,
biodegradable polymers can be grouped into two large groups based on their
structure and synthesis. One of these groups is agro-polymers, or those derived
from biomass. The other consists of biopolyesters, which are those derived from
microorganisms or synthetically made from either naturally or synthetic monomers.
Figure 13.6 illustrates the organization of biodegradable polymers based on their
structure and occurrence.
Fig. 13.6 Biodegradable Polymers
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Agro-polymers include polysaccharides, like starches found in potatoes or wood, Solar Energy
and proteins, such as animal based whey or plant derived gluten. Polysaccharides and Polymerization
consist of glycosidic bonds, which take a hemiacetal of a saccharide and binds it
to an alcohol by means of loss of water. Proteins are made from amino acids,
which contain various functional groups. These amino acids come together again NOTES
through condensation reactions to form peptide bonds, which consist of amide
functional groups. Examples of biopolyesters include polyhydroxybutyrate and
polylactic acid.
Uses of Biodegradable Polymers (BPs)
Conventional polymers, such as polyethene and polypropylene are durable in nature
can persist for many years after disposal. They are appropriate when used for
products which require a long lifespan, such as plastic tables and chairs, but seem
inappropriate for applications in which plastics are used for short time periods and
then disposed of, such as packaging items.
Furthermore, plastics are often soiled by food and other biological
substances, making physical recycling of these materials impractical and generally
undesirable. In contrast, the biodegradable polymers can be disposed of in prepared
bioactive environments to undergo degradation by the enzymatic actions of
microorganisms, bacteria, algae and fungi.
Their polymer chains may also be broken down by non-enzymatic processes,
such as chemical hydrolysis. The biodegradable polymers are often derived from
plant processing of atmospheric CO2. Biodegradation converts them to CO2,
CH4, water, biomass, humic matter, and other natural substances. Consequently,
the biodegradable polymers are thus naturally recycled by biological processes.
Biodegradable polymers contain polymer chains that are hydrolytically or
enzymatically cleaved, resulting in, soluble degradation products. Biodegradability
is particularly desired in biomedical applications, in which degradation of the
polymer ensures clearance from the body and eliminates the need for retrieval or
explant. Biodegradable polymers have applications in the following areas:
 Controlled/Sustained Release Drug Delivery Approaches
 Tissue Engineering Scaffolds
 Temporary Prosthetic Implant
Check Your Progress

11. What are biodegradable polymers ?
12. Give the uses of biodegradable polymers.
13. What are the applications of biodegradable polymers?
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Solar Energy
Conversion: Polymers 13.6 ATOM RADICAL POLYMERIZATION: BASIC
and Polymerization
MECHANISM AND APPLICATIONS
NOTES Free Radical Polymerization (FRP) is a specific methodology or technique of

polymerization using which a polymer is characteristically formed by the successive
addition of free-radical building blocks. Free radicals can be formed by a number
of different mechanisms, usually involving separate initiator molecules. These free
radical polymers can grow their polymer chains by initiating free radical additions
(non-radical) monomer units, thus following the generation characteristics.
Free radical polymerization is a key synthesis route for obtaining a wide
variety of different polymers and complex material. The relatively non-specific
nature of free radical chemical interactions makes this one of the most versatile
forms of polymerization available and allows facile reactions of polymeric free
radical chain ends and other chemicals or substrates.
Fundamentally, the free radical polymerization is an exceptional type of chain
growth polymerization along with anionic, cationic and coordination polymerization.
IUPAC Definition
Free Radical Polymerization (FRP) is a chain polymerization in which the kinetic
chain carriers are radicals. Usually, the growing chain end bears an unpaired electron.
Atom Transfer Radical Polymerization (ATRP)
At present, the Atom Transfer Radical Polymerization (ATRP) is one of the most
frequently used synthetic polymerization methods/techniques for preparing well-
defined polymers with complex architecture.
Characteristically, the Atom Transfer Radical Polymerization (ATRP) is an example
of a reversible-deactivation radical polymerization. Similar to its equivalent form
Atom Transfer Radical Addition (ATRA), the ATRP is also a methodology of
forming a carbon-carbon bond with a transition metal catalyst. The polymerization
that occurs using this method is termed as Atom Transfer Radical Addition
Polymerization (ATRAP). As the name implies, the atom transfer step is crucial in
the reaction responsible for uniform polymer chain growth. ATRP or transition
metal-mediated living radical polymerization was independently discovered by
Mitsuo Sawamoto and by Krzysztof Matyjaszewski in 1995.
IUPAC Definition for ATRP
The Atom Transfer Radical Polymerization (ATRP) is a controlled reversible-
deactivation radical polymerization in which the deactivation of the radicals involves
reversible atom transfer or reversible group transfer catalyzed usually, though not
exclusively, by transition-metal complexes.
The following structure illustrates a typical ATRP reaction in which ‘A’ is Initiation,
‘B’ is Equilibrium with dormant species and ‘C’ is Propagation.
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Solar Energy
and Polymerization
NOTES
Generally, the ATRP uses a transition metal complex as the catalyst with an
alkyl halide as the initiator (R-X). Various transition metal complexes, specifically
Cu, Fe, Ru, Ni, and Os are typically used as catalysts for ATRP. In an ATRP
process, the dormant species is activated by the transition metal complex for
generating radicals through one electron transfer process. Simultaneously the
transition metal is oxidized to the forms having higher oxidation state. This reversible
process rapidly establishes an equilibrium that is predominately shifted to the side
with very low radical concentrations. The number of polymer chains is determined
by the number of initiators. Each growing chain has the same probability to
propagate with monomers to form living/dormant polymer chains (R - Pn - X).
Consequently this results in the formation of polymers with similar molecular weights
and narrow molecular weight distribution.
ATRP reactions are very robust in nature as they have many functional groups,
such as allyl, amino, epoxy, hydroxy, and vinyl groups present in either the monomer
or in the initiator. ATRP methods are also advantageous because of their easy
preparation methods, commercial availability and use of inexpensive catalysts
(copper complexes), pyridine-based ligands, and initiators (alkyl halides).
Components of Normal ATRP
There are five important variable components of ATRP or Atom Transfer Radical
Polymerizations, namely the monomer, initiator, catalyst, ligand, and solvent.
Monomer: Monomers that are typically used in ATRP are the molecules with
substituents that can stabilize the propagating radicals, for example styrenes,
(meth)acrylates, (meth)acrylamides and acrylonitrile. ATRP can successfully form
the polymers with high number average molecular weight and low dispersity when
the concentration of the propagating radical balances the rate of radical termination.
However, the propagating rate is unique to each individual monomer. Therefore, it
is significant that the other components of the polymerization, i.e., the initiator,
catalyst, ligand, and solvent must be optimized in order for the concentration of
the dormant species to be greater than that of the propagating radical. It has to be
low enough in order to prevent slowing down or halting the reaction.
Initiator: The number of growing polymer chains is determined by the initiator.
To safeguard or maintain a low poly-dispersity and a controlled polymerization,
the rate of initiation must be faster than the rate of propagation. Preferably, all the
polymer chains will be initiated in a very short period of time and will be propagated
at the same rate. Initiators are typically selected to be alkyl halides whose
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Material 265
Solar Energy frameworks are similar to that of the propagating radical. Alkyl halides, such as
and Polymerization alkyl bromides are more reactive as compared to alkyl chlorides. Both offer good
molecular weight control. The shape or structure of the initiator influences polymer
architecture. For example, initiators with multiple alkyl halide groups on a single
NOTES core can lead to a star-like polymer shape. Furthermore, -functionalized ATRP
initiators can be used to synthesize hetero-telechelic polymers with a variety of
chain-end groups. Figure 13.7 illustrates the star initiator for ATRP.
Fig. 13.7 Star Initiator for ATRP
Catalyst: The catalyst is considered as the most significant component of ATRP

because it determines the equilibrium constant between the active and dormant
species. This equilibrium basically determines the rate of polymerization. An
equilibrium constant that is too small may inhibit or slow the polymerization while
an equilibrium constant that is too large leads to a wide distribution of chain lengths.
Following are the prerequisites for the metal catalyst:
 There has to be two accessible oxidation states which are differentiated by
one electron.
 The metal center must essentially have reasonable affinity for halogens.
 The coordination sphere of the metal must essentially be expandable when
it is oxidized for accommodating the halogen.
 The transition metal catalyst should not lead to significant side reactions,
such as irreversible coupling with the propagating radicals and catalytic radical
termination.
The most considered catalysts include copper which has revealed the most versatility
and adaptability with successful polymerizations for a wide range of monomers.
Ligand: One of the most essential characteristics in an ATRP reaction is the precise
selection of ligand which is used in combination with the traditionally copper halide
catalyst to form the catalyst complex. The main function of the ligand is to solubilize
the copper halide in whichever solvent is selected and to adjust or regulate the
redox potential of the copper.
This changes the activity and dynamics of the halogen exchange reaction
and subsequent activation and deactivation of the polymer chains during
Self-Instructional polymerization. Consequently it significantly affects the kinetics of the reaction
266 Material
and also the degree of control over the polymerization. Different types of ligands Solar Energy
are selected or preferred based on the characteristics of the monomer and the and Polymerization
preferred metal for the catalyst, such as the copper halides are principally used as
the catalyst while the amine based ligands are mostly used. However, a too active
catalyst can cause loss of control and can also increase the polydispersity of the NOTES
resulting polymer.
Solvents: The commonly used solvents include Toluene, 1,4-Dioxane, Xylene,
Anisole, DMF (Dimethylformamide), DMSO (Dimethyl Sulfoxide), Water,
Methanol, Acetonitrile, or even the Monomer itself.
Applications
Free radical polymerization is significantly used in the manufacturing of polystyrene,
thermoplastic block copolymer elastomers, cardiovascular stents, chemical
surfactants and lubricants. Block copolymers are typically used for a wide variety
of applications including adhesives, footwear and toys.
In addition, the free radical polymerization has applications in research, such as in
the functionalization of carbon nanotubes. Chain growth polymerization typically
synthesizes a polymer with predetermined properties.
13.6.1 Dendrimer
Dendrimers are repetitively branched molecules. The name ‘Dendrimers’ comes
from the Greek word ‘Dendron’ which defines ‘tree’. Synonymous terms for
dendrimer are arborols and cascade molecules. The first dendrimers were made
by divergent synthesis approaches by Fritz Vögtle in 1978, R.G. Denkewalter at
Allied Corporation in 1981, Donald Tomalia at Dow Chemical in 1983 and in
1985, and by George R. Newkome in 1985. In 1990, a convergent synthetic
approach was introduced by Craig Hawker and Jean Fréchet.
Typically, a dendrimer is symmetric around the core and often adopts a
spherical three-dimensional morphology. The word dendron also come across
frequently. A dendron usually contains a single chemically addressable group called
the focal point or core. The difference between dendrons and dendrimers is
illustrated in the Figure 13.8, but both the terms typically spill upon interchangeably.
Fig. 13.8 Dendrimer and Dendron

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Solar Energy Dendritic molecules are characterized on the basis of structural precision.
and Polymerization Fundamentally, both the ‘Dendrimers’ and ‘Dendrons’ are monodisperse and
typically highly symmetric spherical compounds. The dendritic molecules can be
approximately divided into two species, low-molecular weight dendritic molecules
NOTES and high-molecular weight dendritic molecules. The first category includes
dendrimers and dendrons, while the second category includes dendronized
polymers, hyperbranched polymers, and the polymer brush.
The properties of dendrimers are usually dominated by the functional groups
on the molecular surface, though, there are some examples of dendrimers which
exhibit internal functionality. It is possible to produce water-soluble dendrimers,
contrasting most of the polymers.
Other manageable properties of dendrimers include toxicity, crystallinity,
tecto-dendrimer formation, and chirality.
Dendrimers are also classified by generation (Refer Figure 13.8). Figure
13.9 illustrates a first generation ‘cyanostar’ dendrimer.
Fig. 13.9 First Generation ‘Cyanostar’ Dendrimer
When the dendrimers are classified by generation, then it refers to the number of
repeated branching cycles that are performed during its synthesis. For example, if
a dendrimer is made by convergent synthesis (Refer Figure 13.10), and the
branching reactions are performed onto the core molecule three times, the resulting
dendrimer is considered a third generation dendrimer. Each successive generation
results in a dendrimer roughly twice the molecular weight of the previous generation.
Higher generation dendrimers have more exposed functional groups on the surface,
which can be typically used to customize the dendrimer for a specific application.
Figure 13.10 illustrates the synthesis of dendrimer into second generation dendrimer
form arborol.
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Solar Energy
and Polymerization
NOTES
Fig. 13.10 Synthesis to Second Generation Form Arborol
Applications
Applications of dendrimers typically defined on the characteristic features that
include how they conjugate other chemical species to the dendrimer surface that
can function as detecting agents, such as a dye molecule, affinity ligands, targeting
components, radio-ligands, imaging agents, or pharmaceutically active compounds.
Dendrimers have very strong potential for these applications because their structure
can lead to multivalent systems. Carboxylic acid and phenol-terminated water-
soluble dendrimers were synthesized to establish their utility in drug delivery as
well as conducting chemical reactions.
Dendrimers can also be used as a solubilizing agent. Typically, the dendrimers with
hydrophobic core and hydrophilic periphery exhibit micelle-like behaviour and
have container properties in solution.
Check Your Progress

14. What is FRP?
15. What is ATRP?

QUESTIONS
1. A polymer is a large molecule or a macromolecule composed of many

repeated subunits.
2. The term ‘Polymer’ was coined in 1833 by Jöns Jacob Berzelius, though
with a definition distinct from the modern IUPAC definition. The modern
concept of polymers as covalently bonded macromolecular structures was
proposed in 1920 by Hermann Staudinger, who spent the next decade
finding experimental evidence for this hypothesis.
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Solar Energy 3. Macromolecule is termed as a molecule of high relative molecular mass, the
and Polymerization structure of which essentially comprises the multiple repetition of units derived,
actually or conceptually, from molecules of low relative molecular mass.
4. Polymers are of two types, naturally occurring polymers and synthetic or
NOTES
man-made polymers. Natural polymers include hemp, shellac, amber, wool,
silk and natural rubber. In addition, the natural polymer cellulose is the main
constituent of wood and paper, while synthetic polymers include polyethylene,
polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol
formaldehyde resin (or Bakelite), neoprene, nylon, polyacrylonitrile, PVB,
silicone, and many more. Million tons of these polymers are made every
year.
5. Conductive polymers are prepared using various methods. Most of the
conductive polymers are prepared by oxidative coupling of monocyclic
precursors. Such reactions entail dehydrogenation as shown below:
6. There are two main methods used in the synthesis of conductive polymers,
namely the chemical synthesis method and the electro (co)polymerization
method.
7. Following are some applications of conductive polymers:
 Provide electromagnetic shielding of electronic circuits.
 Used as antistatic coating material to prevent electrical discharge
exposure on photographic emulsions.
 Used as hole injecting electrodes for OLEDs (Organic Light Emitting
Devices).
8. Following are the properties of polymer electrolyte:
 Adequate conductivity for practical purposes
 Low electronic conductivity
 Good mechanical properties
 High chemical, electrochemical and photochemical stability
 Ease of processing
9. Gel electrolyte is formed by dissolving salt in polar liquid and adding inactive
polymeric material.
10. Plasticized electrolyte is fundamentally a gel electrolyte but is typically
associated with the addition of small amounts of a high dielectric constant
solvent which enhances its conductivity.
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270 Material
11. Biodegradable polymers tend to consist of ester, amide or ether bonds. In Solar Energy
general, biodegradable polymers can be grouped into two large groups and Polymerization
based on their structure and synthesis.
12. Conventional polymers, such as polyethene and polypropylene are durable
NOTES
in nature can persist for many years after disposal. They are appropriate
when used for products which require a long lifespan, such as plastic tables
and chairs, but seem inappropriate for applications in which plastics are
used for short time periods and then disposed of, such as packaging items.
13. Biodegradable polymers have applications in the following areas:
 Controlled/Sustained Release Drug Delivery Approaches
 Tissue Engineering Scaffolds
 Temporary Prosthetic Implant
14. Free Radical Polymerization (FRP) is a specific methodology or technique
of polymerization using which a polymer is characteristically formed by the
successive addition of free-radical building blocks.
15. Atom Transfer Radical Polymerization (ATRP) is one of the most frequently
used synthetic polymerization methods/techniques for preparing well-defined
polymers with complex architecture.
13.8 SUMMARY
 The term ‘Polymer’ is derived from the Greek word ‘Polus’ meaning ‘many,
much’ and ‘Meros’ meaning ‘part’. Principally it refers to a molecule whose
structure is composed of multiple repeating units, from which originates a
characteristic of high relative molecular mass and attendant properties
 Both the synthetic and the natural polymers essentially have diverse roles in
our day-to-day life, because of their extensive properties. Polymers range
from familiar synthetic plastics, such as polystyrene to natural biopolymers,
such as DNA (Deoxyribo Nucleic Acid) and proteins that are fundamental
units to biological structure and function.
 Polymers are defined as any of a class of natural or synthetic substances
composed of very large molecules, called macromolecules that are multiples
of simpler chemical units called monomers.
 A molecule of high relative molecular mass, the structure of which essentially
comprises the multiple repetition of units derived, actually or conceptually,
from molecules of low relative molecular mass.
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Solar Energy
 Polymers are specifically defined on the basis of biophysics and
and Polymerization macromolecular science, and polymer science (which includes polymer
chemistry and polymer physics).
NOTES  Natural polymers include hemp, shellac, amber, wool, silk and natural
rubber. In addition, the natural polymer cellulose is the main constituent of
wood and paper.
 Synthetic polymers include polyethylene, polypropylene, polystyrene,
polyvinyl chloride, synthetic rubber, phenol formaldehyde resin (or Bakelite),
neoprene, nylon, polyacrylonitrile, PVB, silicone, and many more. Million
tons of these polymers are made every year.
 Polymer synthesis, also called polymerization, is the process by which
monomers (small molecules) are covalently bonded to form a usually long
chain of polymer.
 Polymerization is, thus, the process of combining many small molecules
termed as monomers into a covalently bonded chain or network.
 Plastic containers of all shapes and sizes are light weight and economically
less expensive than the more traditional containers. Clothing, floor coverings,
garbage disposal bags, and packaging are other polymer applications.
 Polyaniline was first described in the mid-19th century by Henry Letheby,
who investigated the electrochemical and chemical oxidation products of
aniline in acidic media. He noted that reduced form was colourless but the
oxidized forms were of deep blue colour.
 Fire safe polymers are particular type of polymers that are resistant to
degradation at high temperatures. The fire resistant polymers are essentially
required in the construction of small, enclosed spaces, such as skyscrapers,
boats, and airplane cabins.
 The purpose is to control heat below the critical level. To achieve this, an
endothermic environment is created for producing non-combustible products,
or the chemicals are added that would remove fire propagating radicals,
such as H and OH, etc.
 Polymers are found everywhere on the earth. Most of the polymers that are
used on an everyday basis are obtained from petroleum-based products.
 The biodegradable polymer are those polymers which can decompose under
aerobic or anaerobic conditions because of the action of microorganism/
enzymes. The materials develop it like starch, cellulose, and polyesters.
Aliphatic polyesters are the most commonly used polymers of this type.
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Solar Energy
 Free Radical Polymerization (FRP) is a chain polymerization in which the Conversion: Polymers
kinetic chain carriers are radicals. Usually, the growing chain end bears an and Polymerization
unpaired electron.
 Monomers that are typically used in ATRP are the molecules with substituents NOTES
that can stabilize the propagating radicals, for example styrenes,
(meth)acrylates, (meth)acrylamides and acrylonitrile.
 The commonly used solvents include Toluene, 1,4-Dioxane, Xylene, Anisole,
DMF (Dimethylformamide), DMSO (Dimethyl Sulfoxide), Water, Methanol,
Acetonitrile, or even the Monomer itself
13.9 KEY WORDS
 Polymer: Polymer is a substance composed of macromolecules also termed

as polymer molecules.
 Macromolecule: A molecule of high relative molecular mass, the structure
of which essentially comprises the multiple repetition of units derived, actually
or conceptually, from molecules of low relative molecular mass.
 Thermogravimetry: The thermogravimetry is a significant technique used
to evaluate the thermal stability of the polymer.
 Rheology: It is a technique used to characterize the flow and deformation
behaviour. It can be used to determine the viscosity, modulus, and other
rheological properties.
 Scattering techniques: The scattering techniques, such as static light
scattering and small-angle neutron scattering are typically used to determine
the dimensions (radius of gyration) of macromolecules in solution or in the
melted state.
 Atom Transfer Radical Polymerization (ATRP) : Atom Transfer Radical
Polymerization (ATRP) is one of the most frequently used synthetic
polymerization methods/techniques for preparing well-defined polymers with
complex architecture.

EXERCISES

1. Brief a note on polymers.
2. Give the structure of polymer.
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Material 273
Solar Energy 3. Give a reaction for polymerization of etehne into polyethene.
and Polymerization 4. What is scattering technique?
5. Give some features of polymers.
NOTES 6. Give the fundamentals of polymer electrolyte.
7. Write a short note on ATRP.
1. Write a detailed note on solar energy conversion, giving its definitions,
structure, techniques, characters and the relevant diagrams.
2. Give a detailed note on conducting polymers mentioning about its types,
synthesis and applications.
3. Elaborate a detailed note on polymer electrolyte and fire retardant polymer.
4. Discuss about thermally stable and biodegradable polymers giving its structure
and uses as well.
5. Explain in detail about the basics of atom radical polymerization its
mechanism and applications.

& Company Ltd.
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Solar Energy
UNIT 14 SOLAR ENERGY Conversion:

Basic Principles
CONVERSION: BASIC
NOTES
PRINCIPLES
Structure
14.0 Introduction
14.1 Objectives
14.2 Solar Energy Conversion: Basics And Principles
14.2.2 Principle of Solar Energy: The Photovoltaic Cell Effect Mechanism
14.3 Solar Panel and Photovoltaic Cell
14.4 Artificial Photosynthesis
14.6 Summary
14.7 Key Words
14.0 INTRODUCTION
Solar energy has amazing potentials. The amount of sunlight that strikes the surface
of the Earth in an hour and a half is sufficient for handling the energy consumption
of the entire world for a full year. Solar energy conversion defines technologies
which are specifically dedicated to the transformation of solar energy to other
(useful) forms of energy including electricity, fuel and heat. It includes technologies,
such as traditional semiconductor photovoltaic devices (PVs), emerging
photovoltaics, and solar fuel generation via electrolysis, artificial photosynthesis
and related forms of photocatalysis which function on basis of the generated energy
rich molecules.
Since the solar energy is a natural form of energy produced from the powerful
heat and light derived from the sun, hence it is an inexpensive source of energy as
it is obtained from a natural source. Solar energy is very convenient to use during
summer season when the sun rays are very strong and therefore a lot of solar
energy can be generated. Furthermore it is a clean source of energy since it is
created direct from the sun.
In this unit, you will study about the concept of solar energy conversion, its
basics and principles, solar panel and photovoltaic cell and artificial photosynthesis
in detail.
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Solar Energy
Conversion: 14.1 OBJECTIVES
Basic Principles

NOTES  Understand the concept of solar energy conversion, its basics and principles
 Discuss about solar panel and photovoltaic cell
 Explain artificial photosynthesis
14.2 SOLAR ENERGY CONVERSION: BASICS AND

PRINCIPLES
Solar energy is radiant light and heat from the Sun that is harnessed using a range
of ever-evolving technologies such as solar heating, photovoltaics, solar thermal
energy, solar architecture, molten salt power plants and artificial photosynthesis.
Solar is the Latin word for ‘Sun’ which is considered as a powerful source of
energy that can be used for heating, cooling and lighting the homes and other
commercial centers.
Solar energy has amazing potentials. The amount of sunlight that strikes the
surface of the Earth in an hour and a half is sufficient for handling the energy
consumption of the entire world for a full year.
There are numerous technologies that are used for converting sunlight into
usable energy form for our day-today usages either for domestic or for commercial
purposes. The most commonly used solar technologies for homes and industries
or commercials are solar water heating, passive solar design for space heating and
cooling, and solar photovoltaics for electricity.
Solar energy conversion defines technologies which are specifically dedicated
to the transformation of solar energy to other (useful) forms of energy including
electricity, fuel and heat. It includes technologies, such as traditional semiconductor
PhotoVoltaic devices (PVs), emerging photovoltaics, and solar fuel generation
via electrolysis, artificial photosynthesis and related forms of photocatalysis which
function on basis of the generated energy rich molecules.
Photovoltaics directly convert solar energy into electricity. They work on
the principle of the photovoltaic effect. When certain materials are exposed to
light, they absorb photons and release free electrons. Based on the principle of
photovoltaic effect, solar cells or photovoltaic cells are made.
Solar energy systems are of different forms, shapes and sizes, such as the
residential systems are installed on the rooftops of the houses while the businesses
or commercial centers install the solar panels according to the requirement to
offset or balance their energy costs. In addition the most significant utility of solar
plant is that it can accommodate a larger group of customers by building huge
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solar power plants to provide cleaner energy to all customers connected to the Solar Energy
Conversion:
grid. Basic Principles
Basically, there are two main types of solar energy technologies, the
PhotoVoltaic (PV) and Concentrating Solar Power (CSP). The PhotoVoltaic or
NOTES
PV solar energy technology is the most common type and is generally utilized in
solar panels. When the sun shines then the sun rays fall directly onto a solar panel.
The photons from the sunlight are absorbed by the cells in the solar panel, which
creates an electric field across the layers and causes electricity to flow. The second
solar energy technology is Concentrating Solar Power or CSP. Principally, it is
used in very large power plants and is only used for commercial purposes and is
therefore not at all appropriate or applicable for residential use. This technology
uses mirrors for reflecting and concentrating sunlight onto solar receivers that collect
solar energy and first convert it into heat energy, which can then be used for
producing electricity.
The natural form of energy is available or obtainable from the solar source
which is quite enormous. The sun provides 1.2 × 105 TW of power onto the Earth
which is the amount that exceeds any other energy reserve or source by means of
capacity and availability. Terawatt (TW) is a metric measurement unit of power
and one terawatt is equal to one trillion watts (1012W).
The sun supplies 1.7 × 1022 Joules of energy to the Earth in just 1.5 days in
the form of solar radiation. For utilization/consumption, this solar radiation has to
be essentially converted into other forms of energy, such as electricity or usable
heat using the efficient technologies.
The solar radiation comprises of,
 Solar energy is electromagnetic radiation.
 Main components (Refer Figure 14.1) of solar radiation as per the
electromagnetic spectrum include the following:
o Infrared ( 52 – 55% > 700 nm)
o Visible (42-43% 400 < < 700 nm)
o Ultraviolet (3-5% 100 < < 400 nm)
 Solar radiation near the earth surface is essentially in the range 290 –
2500 nm.
 Quantum (unit energy) of electromagnetic radiation is defined as ‘Photon
(E = hv)’ which is specifically used in the mechanism of solar conversion.
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Solar Energy
Conversion:
Basic Principles
NOTES
Fig. 14.1 Solar Radiation in the Electromagnetic Spectrum

(Courtesy: Wikimedia Commons)
Figure 14.1 illustrates all the existing forms of electromagnetic radiation across the
scale of radiation wave length and frequency. The solar radiation that reaches the
surface of the Earth predominantly consists of infrared radiation (52-55%), visible
radiation (42-43%) and ultraviolet radiation (3-5%) which specifically comes under
the wave length range from ~ 290 nm to 2.5 m.
The different types of electromagnetic radiation permits the sunlight to be converted
into solar energy form through the following physical mechanisms:
 Direct Conversion to Electricity - Through Photovoltaic Effect
 Conversion to Usable Heat - Through Thermal Collectors
 Conversion to Matter / Fuel - Production of Biomass Through
Photosynthesis
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Factors Determining the Amount of Solar Energy Generation Solar Energy
Conversion:
Since the solar energy is a natural form of energy produced from the powerful heat Basic Principles
and light derived from the sun, hence it is an inexpensive source of energy as it is
obtained from a natural source. Solar energy is very convenient to use during
NOTES
summer season when the sun rays are very strong and therefore a lot of solar
energy can be generated. Furthermore it is a clean source of energy since it is
created direct from the sun.
For obtaining maximum amount of solar energy, the solar heaters or solar
panels should be placed in a location where the solar rays can reach the panels
effectively so as to generate a lot of power. This could be on top of the roof,
where there is no shadow that can hinder the electromagnetic rays from reaching
the solar panels. The solar energy production, i.e., the amount of power that can
be generated, however, is significantly determined by the season of the year. During
the winter season only small amount of solar energy can be generated because the
Earth is far from the sun and therefore only less concentrated amount of solar
energy is received by the solar panels. In the cold season, the sun rays are very
minimal and are very scattered so they cannot reach the solar panels directly.
Secondly, the time of the day also plays an important role. In the afternoon hours
when it is extremely hot, then a lot of solar energy can be generated which can be
used for several days.
In addition, the geographical location of the house or commercial complex
also has important role in the amount of solar energy that can be generated. The
other factors that affect in the production of amount of solar energy are air pollutants,
clouds, and the amount of water vapor, dust and air molecules.
Solar electric systems use solar cells for converting the radiant energy of Sun into
the consumable electricity form. The principle technology used is termed as the
photovoltaic effect. Because a solar cell can merely generate approximately 1-2
Watts of power, therefore it is essential to associate/combine the solar cells into
the solar power panels so that more power can be generated.
Nowadays the solar technologies, such as the ‘Solar Power’ and the ‘Solar
Panels’ are widely used for generating ‘Solar Energy’ to overcome energy crisis.
Solar energy is also sometimes termed as photovoltaic energy. Following are the
basic principles of solar energy conversion technology or methodology.
Solar Cells: A solar panel is made of several photovoltaic cells which are very
thin, about 1/100th of an inch thick and usually 3 to 4 inches square. These cells
are capable of converting sunlight into energy form through the photovoltaic effect.
The most significant feature of the solar cells is that they do not require any type of
fuel for their function and have a standard lifetime of approximately 20-30 years.
Solar Panels and Solar Modules: Photovoltaic (PV) cells are characteristically
organized and assembled together for creating a solar module. The solar module
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Solar Energy is specifically formed of solar panels. About 2 to 200 cells are assembled together
Conversion:
Basic Principles to form a solar module which is enclosed in tempered glass and aluminum which
protect them from weather conditions, thus making them weather resistant.
Assembling Solar Cells: Similar to batteries, the solar cells are either combined
NOTES
in series or in parallel for creating higher and more specified voltages and amperages.
For example, four 1-volt/1-amp solar cells in series will produce 4 volts, but the
amperage will halt at 1 amp. On the other hand, four 1-volt/1-amp solar cells in
parallel will produce 1 volt but have minimum 4 amperages of output. The amperage
can be multiplied by the wattage for obtaining the generated watts. A watt is a
measure of energy, for example a common 40 watt light bulb.
Sizes and Shapes: The solar modules can be made/produced in a various sizes
and shapes as per the requirement defined in the installation and application
specifications. Solar panels are available in standard rectangular, triangular, foldable,
and even in the form of thin-film rolls. Due to these specifications, the solar panels
have their usage in a wide range of applications, such as space stations, auto
motives, lights, pools, heaters, electronic gadgets, and many more.
Solar Array: The solar modules are combined together for creating solar arrays.
Principally, a solar array is a group of solar modules which are specifically designed
and assembled together to meet a certain electrical load. The solar arrays can be
seen mounted on the rooftops of homes or commercial complexes..
AC vs DC: The solar panels generate Direct Current (DC) electricity. Basically,
most of the household electronics and the electrical power grid are designed to
take Alternating Current (AC) power. Therefore, the electricity that is generated
from the solar array must be converted to AC if it is to be used at home. This is
done with the help of an inverter, which takes the DC power and converts it into
the AC power. The devices which use the DC power, such as certain lights,
batteries, special devices, etc., then there is no need of an inverter.
14.2.2 Principle of Solar Energy: The Photovoltaic Cell Effect
Mechanism
The Photovoltaic (PV) cell effect is defined as the conversion of sunlight energy
into electricity. In a photovoltaic system, the photovoltaic cells implement this effect.
Semi-conducting materials in the photovoltaic cell are doped for forming p-n
structure as an internal electric field, as shown in Figure 14.2. The p-type (positive)
silicon has the tendency to give up electrons and to gain holes while the n-type
(negative) silicon accepts electrons. When sunlight hit the photovoltaic cell, then
the photons in light excite some of the electrons in the semiconductors to become
electron-hole, i.e., the negative-positive pairs. Subsequently there is an internal
electric field as these pairs are induced to separate. As a consequence, the electrons
move to the negative electrode while the holes move to the positive electrode. A
conducting wire connects the negative electrode, the load, and the positive electrode
in series to form a complete circuit. Consequently, an electric current is generated
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to supply the external load. Using this method the photovoltaic effect mechanism Solar Energy
Conversion:
works in a solar cell. Basic Principles
NOTES
Fig. 14.2 The p-n Structure as an Internal Electric Field
Check Your Progress

1. Define solar energy.
2. How does photovoltaics work?
3. How much power does sun provides to earth.
14.3 SOLAR PANEL AND PHOTOVOLTAIC CELL
The ‘Photovoltaic (PV) Solar Panels’ absorb sunlight as a source of energy to

generate electricity. A photovoltaic module is a packaged, connected assembly of
typically 6 × 10 photovoltaic solar cells (Refer Figure 14.3). Photovoltaic modules
constitute the photovoltaic array of a photovoltaic system that generates and supplies
solar electricity for commercial and residential applications. The most common
application of solar energy is solar water heating systems.
Fig. 14.3 Solar PV Modules

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Solar Energy Photovoltaic modules use light energy (photons) from the Sun to generate
Conversion:
Basic Principles electricity through the photovoltaic effect. The majority of modules use wafer-
based crystalline silicon cells or thin-film cells. The structural (load carrying) member
of a module can either be the top layer or the back layer. Cells must also be
NOTES protected from mechanical damage and moisture. Most modules are rigid, but
semi-flexible ones based on thin-film cells are also available. The cells must be
connected electrically in series, one to another.
A PV junction box is attached to the back of the solar panel and it is its
output interface. Externally, most of photovoltaic modules use MC4 connectors’
type to facilitate easy weatherproof connections to the rest of the system. Solar
module electrical connections are made in series to achieve a desired output voltage
or in parallel to provide a desired current capability (amperes). The conducting
wires that take the current off the modules may contain silver, copper or other
non-magnetic conductive transition metals. Bypass diodes may be incorporated
or used externally, in case of partial module shading, to maximize the output of
module sections still illuminated. Figure 14.4 illustrates the mechanism that how
the solar energy is generated and supplied using the solar cell and a PV system. A
single solar module can produce only a limited amount of power, hence most
installations contain multiple modules. A photovoltaic system typically includes an
array of photovoltaic modules, an inverter, and the battery pack for storage,
interconnection wiring, and optionally a solar tracking mechanism.
Fig. 14.4 Mechanism - Solar Cell to a PV System
Some special solar PV modules include concentrators in which light is

focused by lenses or mirrors onto smaller cells. This enables the use of cells with a
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high cost per unit area, such as gallium arsenide in a cost-effective way. Solar Solar Energy
Conversion:
panels may also use metallic frames consisting of racking components, brackets, Basic Principles
reflector shapes, and troughs that enhance the panel structure.
Solar Cell or Photovoltaic Cell
NOTES
A solar cell or photovoltaic cell is an electrical device that converts the energy of
light directly into electricity by the photovoltaic effect, which is a physical and
chemical phenomenon. It is a form of photoelectric cell, defined as a device whose
electrical characteristics, such as current, voltage, or resistance, vary when exposed
to light. Individual solar cell devices can be combined to form modules, otherwise
known as solar panels. In basic terms a single junction silicon solar cell can produce
a maximum open-circuit voltage of approximately 0.5 to 0.6 volts. Figure 14.5
illustrates the standard symbol of a photovoltaic cell or a solar cell.
Fig. 14.5 Symbol of a Photovoltaic Cell
Solar cells are described as being photovoltaic, irrespective of whether the source
is sunlight or an artificial light. They are used as a photodetector, for example
infrared detectors, detecting light or other electromagnetic radiation near the visible
range or measuring light intensity. The operation of a photovoltaic (PV) cell requires
following three basic attributes:
 The absorption of light, generating either electron-hole pairs.
 The separation of charge carriers of opposite types.
 The separate extraction of those carriers to an external circuit.
In contrast, a solar thermal collector supplies heat by absorbing sunlight, for the
purpose of either direct heating or indirect electrical power generation from heat.
While a ‘photoelectrolytic cell’ or photoelectrochemical cell refers either to a type
of photovoltaic cell or to a device that splits water directly into hydrogen and
oxygen using only solar illumination.
Figure 14.6 illustrates a conventional crystalline silicon solar cell. Electrical contacts
made from busbars (the larger silver-colored strips) and fingers (the smaller ones)
are printed on the carbon wafer.
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Solar Energy
Conversion:
Basic Principles
NOTES
Fig. 14.6 A Conventional Crystalline Silicon Solar Cell
Relationship between Solar Cells, Solar Modules, Solar Panels and Solar
Arrays or Systems
Multiple solar cells in an integrated group, all oriented in one plane, constitute a
solar photovoltaic panel or solar module. Photovoltaic modules often have a sheet
of glass on the sun-facing side, allowing light to pass while protecting the
semiconductor wafers. Solar cells are usually connected in series and parallel
circuits or series in solar modules, creating an additive voltage. Connecting solar
cells in parallel yields a higher current; however, problems, such as shadow effects
can shut down the weaker (less illuminated) parallel string (a number of series
connected cells) causing substantial power loss and possible damage because of
the reverse bias applied to the shadowed cells by their illuminated associates.
Although solar modules can be interconnected for creating the solar array with the
desired peak DC voltage and loading current capacity, using independent MPPTs
(Maximum Power Point Trackers). Otherwise, shunt diodes can reduce shadowing
power loss in solar arrays with series/parallel connected solar cells.
Space Applications and Solar Cells
NASA used solar cells on its spacecraft from the very beginning. The Explorer 6,
launched in 1959, had four solar arrays that folded out once in orbit. They provided
power for months in space. Solar cells were also used in a prominent application
when they were proposed and flown on the ‘Vanguard Satellite’ in 1958, as an
alternative power source to the primary battery power source. By adding solar
cells to the outside of the body, the mission time could be extended with no major
changes to the spacecraft or its power systems. In 1959 the United States launched
Explorer 6, featuring large wing-shaped solar arrays, which became a common
feature in satellites. These arrays consisted of 9600 Hoffman solar cells.
By the 1960s, solar cells became the main power source for most Earth
orbiting satellites and a number of probes into the solar system, since they offered
the best power-to-weight ratio. In the early 1990s the technology used for space
solar cells diverged from the silicon technology used for terrestrial panels, with the
spacecraft application shifting to gallium arsenide-based III-V semiconductor
materials, which then evolved into the modern III-V multijunction photovoltaic
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Dye-Sensitized Solar Cell Solar Energy
Conversion:
A dye-sensitized solar cell (DSSC, DSC, DYSC or Grätzel cell) is a low-cost solar Basic Principles
cell belonging to the group of thin film solar cells. It is based on a semiconductor
formed between a photo-sensitized anode and an electrolyte, a photoelectro-
NOTES
chemical system. The modern version of a dye solar cell, also known as the Grätzel
cell, was originally co-invented in 1988 by Brian O’Regan and Michael Grätzel
at UC Berkeley and this work was later developed by the aforementioned scientists
at the École Polytechnique Fédérale de Lausanne until the publication of the first
high efficiency DSSC in 1991. Michael Grätzel has been awarded the 2010
Millennium Technology Prize for this invention.
Dye-Sensitized Solar Cells (DSSCs) are made of low-cost materials
and do not need elaborate manufacturing equipment, hence easy to manufacture,
i.e., DIY (Do It Yourself) manner. It is significantly less expensive as compared
to older solid-state solar cell designs. DSSC’s can be engineered into flexible
sheets. Though its conversion efficiency is less than the best thin film cells, but
its price/performance ratio is high enough which is making it popular.
Typically a ruthenium metalorganic dye (Ru-centered) is used as a
monolayer of light-absorbing material. The Dye-Sensitized Solar Cell or DSSC
depends on a mesoporous layer of nanoparticulate titanium dioxide to greatly
amplify the surface area, typically 200–300 m 2/g TiO2, as compared to
approximately 10 m2/g of flat single crystal. The photogenerated electrons
from the light absorbing dye are passed on to the n-type TiO2 and the holes
are absorbed by an electrolyte on the other side of the dye. The circuit is
completed by a redox couple in the electrolyte, which can either be a liquid or
a solid. This type of cell allows more flexible use of materials and is typically
manufactured by screen printing or ultrasonic nozzles, with the potential for
lower processing costs than those used for bulk solar cells. However, the
dyes in these cells also suffer from degradation under heat and UV light and
the cell casing is difficult to seal due to the solvents used in assembly.
Check Your Progress

4. What does PV cell use to generate electricity?
5. What does photovoltaic modules constitute of?
6. Define solar cell .
7. What are the attributes required in the operation of a PV cell?
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Solar Energy
Conversion: 14.4 ARTIFICIAL PHOTOSYNTHESIS
Basic Principles
Artificial photosynthesis is a chemical process that bio-mimics the natural

NOTES process of photosynthesis to convert sunlight, water, and carbon dioxide into
carbohydrates and oxygen. The term artificial photosynthesis is commonly
used to refer to any arrangement for capturing and storing the energy from
sunlight in the chemical bonds of a fuel (a solar fuel). Photocatalytic water
splitting converts water into hydrogen and oxygen and is considered as a key
subject of artificial photosynthesis. Light-driven carbon dioxide reduction is
another significant process that replicates natural carbon fixation. The
mechanism includes the direct production of solar fuels, photoelectrochemistry
and its application in fuel cells, and the engineering of enzymes and
photoautotrophic microorganisms for microbial biofuel and biohydrogen
production from sunlight.
The photosynthetic reaction can be divided into two half-reactions of
oxidation and reduction, both are essential for producing fuel. In plant
photosynthesis, water molecules are photo-oxidized to release oxygen and
protons. The second phase of plant photosynthesis, also known as the Calvin-
Benson cycle, is a light-independent reaction that converts carbon dioxide
into glucose (fuel). Furthermore, the protons resulting from water splitting can
be used for hydrogen production. These catalysts must be able to react quickly
and absorb a large percentage of the incident solar photons. Figure 14.7
illustrates the natural (left) and artificial photosynthesis (right) mecahnisms.
Fig. 14.7 Natural (left) versus Artificial Photosynthesis (right)
The photovoltaics can provide energy directly from sunlight, though there
is a limit to it in the inefficiency of fuel production from photovoltaic electricity
(indirect process) due to the fact that sunshine is not constant throughout the
day. The objective of artificial photosynthesis is to produce a fuel from sunlight
that can be stored conveniently and used when sunlight is not available, by
using direct processes, that is, to produce a solar fuel. With the development
of catalysts able to reproduce the major parts of photosynthesis, water and
sunlight would ultimately be the only needed sources for clean energy
production.
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One significant process for the creation of a clean and affordable energy Solar Energy
Conversion:
supply is the development of photocatalytic water splitting under solar light. Basic Principles
This method of sustainable hydrogen production is a major objective for the
development of alternative energy systems. It is also considered as the most
efficient ways of obtaining hydrogen from water. The conversion of solar energy NOTES
into hydrogen through a water-splitting process assisted by photosemiconductor
catalysts is one of the most important technologies. This process has the
potential for generating large quantities of hydrogen in an ecological manner.
In energy terms, natural photosynthesis can be divided into following three
steps:
Step 1: Light-harvesting complexes in bacteria and plants capture photons
and transduce them into electrons, injecting them into the photosynthetic chain.
Step 2: Proton-coupled electron transfer along several cofactors of the
photosynthetic chain, causing local, spatial charge separation.
Step 3: Redox catalysis, which uses the aforementioned transferred electrons
to oxidize water to dioxygen and protons; these protons can in some species
be utilized for dihydrogen production.
Figure 14.8 illustrates a triad assembly, with a Photosensitizer (P) linked in
tandem to a water oxidation Catalyst (D) and a hydrogen evolving Aatalyst
(A). Electrons flow from D to A when catalysis occurs.
Fig. 14.8 Triad Assembly: Photosensitizer (P), Catalyst (D) and Aatalyst (A)
Using biomimetic approaches, artificial photosynthesis tries to construct systems

doing the same type of processes. Ideally, a triad assembly could oxidize
water with one catalyst, reduce protons with another and have a photosensitizer
molecule to power the whole system. One of the simplest designs is where the
photosensitizer is linked in tandem between a water oxidation catalyst and a
hydrogen evolving catalyst (Refer Figure 14.8):
Step 1: The photosensitizer transfers electrons to the hydrogen catalyst when
hit by light, becoming oxidized in the process.
Step 2: This drives the water splitting catalyst to donate electrons to the
photosensitizer. In a triad assembly, such a catalyst is often referred to as a
donor. The oxidized donor is able to perform water oxidation.
The state of the triad with one catalyst oxidized on one end and the
second one reduced on the other end of the triad is referred to as a charge
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Solar Energy separation, and is a driving force for further electron transfer, and consequently
Conversion:
Basic Principles catalysis, to occur. The different components may be assembled in diverse
ways, such as supra-molecular complexes, compartmentalized cells, or linearly,
covalently linked molecules.
NOTES
By studying the natural Oxygen-Evolving Complex (OEC), the specific
catalysts have been developed by researchers, such as the ‘Blue Dimer’ to
mimic its function or inorganic-based materials, such as Birnessite with the
similar building block as the OEC.
Hydrogen Catalysts: Hydrogen is the simplest solar fuel to synthesize, since
it involves only the transference of two electrons to two protons. It must,
however, be done stepwise, with formation of an intermediate hydride anion:
The proton-to-hydrogen converting catalysts present in nature are hydrogenases.

These are enzymes that can either reduce protons to molecular hydrogen or oxidize
hydrogen to protons and electrons. Synthesized catalysts include structural H-
cluster models, a dirhodium photocatalyst, and cobalt catalysts.
Water-Oxidizing Catalysts: Water oxidation is a more complex chemical
reaction than proton reduction. In nature, the Oxygen-Evolving Complex
(OEC) performs this reaction by first accumulating reducing equivalents
(electrons) in a Manganese-Calcium Cluster (MCC) within PhotoSystem II
(PS II), and then delivering them to water molecules, with the resulting
production of molecular oxygen and protons:
Without a natural or artificial catalyst, this reaction is extremely endothermic

and requires high temperatures, at least 2500 K.
The exact structure of the oxygen-evolving complex has been hard to
determine experimentally. Some ruthenium complexes, such as the dinuclear
µ-oxo-bridged ‘Blue Dimer’, the first of its kind to be synthesized, are capable
of light-driven water oxidation. In this situation, the ruthenium complex acts as
both photosensitizer and catalyst. Many metal oxides have been found to have
water oxidation catalytic activity, including Ruthenium(IV) Oxide (RuO2),
Iridium(IV) Oxide (IrO2), Cobalt Oxides (including Nickel-Doped Co3O4),
Manganese Oxide (including layered MnO2 (Birnessite), Mn2O3), and a mixture
of Mn2O3 with CaMn2O4. Oxides can be easily obtained as compared to the
molecular catalysts, especially those obtained from relatively abundant
transition metals (Cobalt and Manganese), but because they observe low
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turnover frequency and slow electron transfer properties, hence their mechanism Solar Energy
Conversion:
of action is hard to decipher and, therefore, to adjust. Basic Principles
In recent times, the Metal-Organic Framework (MOF)-based materials
have been found to be an extremely favourable catalysts for water oxidation
NOTES
with first row transition metals.
Photoelectrochemical Cells: Photoelectrochemical cells are defined as a
heterogeneous system that uses light for producing either electricity or
hydrogen. Most of the photoelectrochemical cells use semiconductors as
catalysts. A favourable and proficient type of solar cell that is evolving nowadays
is the Dye-Sensitized Solar Cell (DSSC). The DSSC cell depends on a
semiconductor, such as, TiO2 for conduction of current on one electrode, but
with a coating of an organic or inorganic dye that acts as a photosensitizer; the
counter electrode is a platinum catalyst for H2 production. These cells have a
self-repair mechanism and solar-to-electricity conversion efficiencies
resembling those of solid-state semiconductors.
Photocatalytic Water Splitting in Homogeneous Systems: Direct water
oxidation by photocatalysts is a more efficient usage of solar energy as
compared to the photoelectrochemical water splitting because it avoids an
intermediate thermal or electrical energy conversion step.
Bio-inspired manganese clusters can efficiently possess water oxidation activity
when adsorbed on clays together with ruthenium photosensitizers, although
with low turnover numbers.
As already discussed in the preceding section that some ruthenium complexes
are capable of oxidizing the water under solar light irradiation. Although their
photostability is still a subject of concern, but many can be reactivated by a
simple adjustment of the conditions in which they work. Enhancement of
catalyst stability has been observed by resorting to polyoxometalates, in
particular ruthenium-based analysis.
The ‘Solar Water Splitting’ or ‘Photocatalytic Water Splitting’ is an artificial
photosynthesis process in which the reaction takes place in the presence of a
photocatalysis in a photoelectrochemical cell specifically used for the dissociation of
water into its constituent parts, Hydrogen (H2) and Oxygen (O2), using either artificial
or natural light. Theoretically, only solar energy (photons), water and a catalyst are
required.
When the solar cells are combined with catalysts and additional functional layers
to form a monolithic photoelectrode as a single block, then splitting of water becomes
very simple. The photocathode is immersed in an aqueous medium and then when the
light falls on it the hydrogen is formed on the front side and oxygen on the back.
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Solar Energy This most significant feature of hydrogen is that it can be stored easily and safely,
Conversion:
Basic Principles and can be used in many different ways whether in a fuel cell to directly generate
electricity and heat, or as feedstock for manufacturing combustible fuels. Nowadays,
the ‘Hydrogen Fuel Production’ is gaining significant importance as oil since other non-
NOTES renewable fuels are becoming gradually exhausted and expensive. The solar water
splitting or photocatalytic water splitting methods are being explored for producing
oxygen and hydrogen, a clean-burning fuel.
Water splitting process holds specific potential since it utilizes water, an inexpensive
renewable resource. Photocatalytic water splitting process uses a catalyst and sunlight
to produce hydrogen out of water.
Methodology of Water Splitting
Whenever the H2O is split into O2 and H2 then the stoichiometric ratio of its products
is determined as 2:1 as per the following reaction:
The process of water splitting is a highly endothermic process (H > 0). Water
splitting occurs naturally in photosynthesis when photon energy is absorbed and
converted into the chemical energy through a complex biological pathway.
For an effective photocatalyst for water splitting, the essential requirement is that
the potential difference (voltage) must be 1.23V at 0 pH. Subsequently, the minimum
band gap for successful water splitting at pH = 0 is 1.23 eV, which corresponds to light
of 1008 nm. These values are true only for a completely reversible reaction at standard
temperature and pressure (1 bar and 25 °C).
Theoretically, the infrared light has sufficient energy to split water into hydrogen
and oxygen, however, this reaction is extremely slow because the wavelength is greater
than 750 nm. The potential must be less than 3.0 V to make efficient use of the energy
present across the full spectrum of sunlight. Water splitting can transfer charges, but not
be able to avoid corrosion for long term stability.
Due to the transparency of water to visible light, the photolysis can only occur
with a radiation wavelength of 180 nm or shorter, under normal conditions. Assuming
a perfect system, the minimum energy input is 6.893 eV.
Materials that are used in photocatalytic water splitting mechanism accomplish
the predefined band requirements and typically have dopants and/or co-catalysts added
to optimize their performance. A sample semiconductor with the proper band structure
is Titanium Dioxide (TiO2). However, due to the relatively positive conduction band of
TiO2, there is little driving force for H2 production, so TiO2 is typically used with a co-
catalyst, such as Platinum (Pt) to increase the rate of H2 production. Most of the
Self-Instructional
290 Material
semiconductors with appropriate band structures for splitting water have the property Solar Energy
Conversion:
to frequently absorb UV light. Since the conduction band is just close to the reference Basic Principles
potential for H2 formation, hence the valence band can be altered to move it closer to
the potential for O2 formation, since there is a greater natural over-potential. NOTES
Electrolysis of water is the decomposition of water into oxygen and hydrogen gas
due to the passage of an electric current. The reaction has a standard potential of
–1.23 V, i.e., it ideally requires a potential difference of 1.23 volts to split water
into oxygen and hydrogen. Using this technique the hydrogen gas and breathable
oxygen can be obtained. Figure 14.9 illustrates the simple setup to demonstrate
the electrolysis of water.
Fig. 14.9 Electrolysis of Water
Reaction Equations
In pure water at the negatively charged cathode, a reduction reaction takes place,
with electrons (e–) from the cathode being given to hydrogen cations to form
hydrogen gas. Figure 14.10 illustrates the overall chemical equation in which the
water is split into hydrogen and oxygen.
Fig. 14.10 Chemical Equation: Water is split into Hydrogen and Oxygen
Self-Instructional
Material 291
Solar Energy The half reaction that is balanced with acid is expressed as:
Conversion:
Basic Principles + − 2
Reduction at Cathode:
NOTES At the positively charged anode, an oxidation reaction occurs, generating oxygen
gas and giving electrons to the anode to complete the circuit and is expressed as:
+ −
Oxidation at Anode: 2 H2O (l) → O2 (g) + 4 H (aq) + 4e
The same half reactions can also be balanced with base as shown below. Not all
the half reactions can be balanced with acid or base. The oxidation or reduction
reaction of water can be balanced. To add half reactions they both must be balanced
with either acid or base. The acid-balanced reactions predominate in acidic (low
pH) solutions, while the base-balanced reactions predominate in basic (high pH)
solutions.
− −
2 2
− −
2 2
On combination even the half reaction pair yields the same overall decomposition
of water into oxygen and hydrogen as follows:
Overall Reaction:
The number of hydrogen molecules produced is thus twice the number of

oxygen molecules. Assuming equal temperature and pressure for both gases, the
produced hydrogen gas has therefore twice the volume of the produced oxygen
gas. The number of electrons pushed through the water is twice the number of
generated hydrogen molecules and four times the number of generated oxygen
molecules.
Check Your Progress

8. Define the term artificial photosynthesis.
9. In how many parts photosynthetic reaction divided?
10. What is a hydrogen catalysts ?
Self-Instructional
292 Material
Solar Energy
14.5 ANSWERS TO CHECK YOUR PROGRESS Conversion:
Basic Principles
QUESTIONS
1. Solar energy is radiant light and heat from the Sun that is harnessed using a NOTES
range of ever-evolving technologies such as solar heating,
photovoltaics, solar thermal energy, solar architecture, molten salt power
plants and artificial photosynthesis.
2. Photovoltaics directly convert solar energy into electricity. They work on
the principle of the photovoltaic effect. When certain materials are exposed
to light, they absorb photons and release free electrons. Based on the
principle of photovoltaic effect, solar cells or photovoltaic cells are made.
3. The sun provides 1.2 × 105 TW of power onto the Earth which is the amount
that exceeds any other energy reserve or source by means of capacity and
availability. Terawatt (TW) is a metric measurement unit of power and one
terawatt is equal to one trillion watts (1012W).
4. The ‘Photovoltaic (PV) Solar Panels’ absorb sunlight as a source of energy
to generate electricity.
5. Photovoltaic modules constitute the photovoltaic array of a photovoltaic
system that generates and supplies solar electricity for commercial and
residential applications.
6. A solar cell or photovoltaic cell is an electrical device that converts the
energy of light directly into electricity by the photovoltaic effect, which is a
physical and chemical phenomenon.
7. The operation of a Photovoltaic (PV) cell requires following three basic
attributes:
 The absorption of light, generating either electron-hole pairs.
 The separation of charge carriers of opposite types.
 The separate extraction of those carriers to an external circuit.
8. Artificial photosynthesis is a chemical process that bio-mimics the natural
process of photosynthesis to convert sunlight, water, and carbon dioxide
into carbohydrates and oxygen.
9. The photosynthetic reaction can be divided into two half-reactions of
oxidation and reduction, both are essential for producing fuel. In plant
photosynthesis, water molecules are photo-oxidized to release oxygen
and protons. The second phase of plant photosynthesis, also known as
the Calvin-Benson cycle, is a light-independent reaction that converts
carbon dioxide into glucose (fuel).
Self-Instructional
Material 293
Solar Energy 10. Hydrogen is the simplest solar fuel to synthesize, since it involves only
Conversion:
Basic Principles the transference of two electrons to two protons. It must, however, be
done stepwise, with formation of an intermediate hydride anion:
NOTES
14.6 SUMMARY
 Solar is the Latin word for ‘Sun’ which is considered as a powerful source
of energy that can be used for heating, cooling and lighting the homes and
other commercial centers.
 Solar energy conversion defines technologies which are specifically
dedicated to the transformation of solar energy to other (useful) forms of
energy including electricity, fuel and heat.
 Solar energy conversion includes technologies, such as traditional
semiconductor photovoltaic devices (PVs), emerging photovoltaics, and
solar fuel generation via electrolysis, artificial photosynthesis and related
forms of photocatalysis which function on basis of the generated energy
rich molecules.
 Photovoltaics directly convert solar energy into electricity. They work on
the principle of the photovoltaic effect. When certain materials are exposed
to light, they absorb photons and release free electrons. Based on the
principle of photovoltaic effect, solar cells or photovoltaic cells are made.
 Solar energy systems are of different forms, shapes and sizes, such as the
residential systems are installed on the rooftops of the houses while the
businesses or commercial centers install the solar panels according to the
requirement to offset or balance their energy costs.
 When the sun shines then the sun rays fall directly onto a solar panel. The
photons from the sunlight are absorbed by the cells in the solar panel, which
creates an electric field across the layers and causes electricity to flow. The
second solar energy technology is Concentrating Solar Power or CSP.
 The sun provides 1.2 × 105 TW of power onto the Earth which is the
amount that exceeds any other energy reserve or source by means of capacity
and availability. Terawatt (TW) is a metric measurement unit of power and
one terawatt is equal to one trillion watts (1012W).
 The sun supplies 1.7 ×1022 Joules of energy to the Earth in just 1.5 days in
the form of solar radiation.
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294 Material
 Solar electric systems use solar cells for converting the radiant energy of Solar Energy
Conversion:
Sun into the consumable electricity form. The principle technology used is Basic Principles
termed as the photovoltaic effect.
 A solar panel is made of several photovoltaic cells which are very thin,
NOTES
about 1/100th of an inch thick and usually 3 to 4 inches square. These cells
are capable of converting sunlight into energy form through the photovoltaic
effect.
 The solar modules can be made/produced in a various sizes and shapes as
per the requirement defined in the installation and application specifications.
Solar panels are available in standard rectangular, triangular, foldable, and
even in the form of thin-film rolls.
 The solar panels generate Direct Current (DC) electricity. Basically, most
of the household electronics and the electrical power grid are designed to
take Alternating Current (AC) power.
 The Photovoltaic (PV) cell effect is defined as the conversion of sunlight
energy into electricity. In a photovoltaic system, the photovoltaic cells
implement this effect. Semi-conducting materials in the photovoltaic cell are
doped for forming p-n structure as an internal electric field.
 The p-type (positive) silicon has the tendency to give up electrons and to
gain holes while the n-type (negative) silicon accepts electrons. When sunlight
hit the photovoltaic cell, then the photons in light excite some of the electrons
in the semiconductors to become electron-hole, i.e., the negative-positive
pairs.
 The ‘Photovoltaic (PV) Solar Panels’ absorb sunlight as a source of energy
to generate electricity. A photovoltaic module is a packaged, connected
assembly of typically 6 × 10 photovoltaic solar cells.
 Photovoltaic modules constitute the photovoltaic array of a photovoltaic
system that generates and supplies solar electricity for commercial and
residential applications.
 Photovoltaic modules use light energy (photons) from the Sun to generate
electricity through the photovoltaic effect. The majority of modules use wafer-
based crystalline silicon cells or thin-film cells.
 A PV junction box is attached to the back of the solar panel and it is its
output interface. Externally, most of photovoltaic modules use MC4
connectors’ type to facilitate easy weatherproof connections to the rest of
the system.
 Solar module electrical connections are made in series to achieve a desired
output voltage or in parallel to provide a desired current capability (amperes).
The conducting wires that take the current off the modules may contain
silver, copper or other non-magnetic conductive transition metals.
Self-Instructional
Material 295
Solar Energy  A photovoltaic system typically includes an array of photovoltaic modules,
Conversion:
Basic Principles an inverter, and the battery pack for storage, interconnection wiring, and
optionally a solar tracking mechanism.
 A solar cell or photovoltaic cell is an electrical device that converts the
NOTES
energy of light directly into electricity by the photovoltaic effect, which is a
physical and chemical phenomenon. It is a form of photoelectric cell, defined
as a device whose electrical characteristics, such as current, voltage, or
resistance, vary when exposed to light.
 Photovoltaic modules often have a sheet of glass on the sun-facing side,
allowing light to pass while protecting the semiconductor wafers. Solar cells
are usually connected in series and parallel circuits or series in solar modules,
creating an additive voltage.
 Dye-Sensitized Solar Cells (DSSCs) are made of low-cost materials
and do not need elaborate manufacturing equipment, hence easy to
manufacture, i.e., DIY (Do It Yourself) manner. It is significantly less
expensive as compared to older solid-state solar cell designs. DSSC’s
can be engineered into flexible sheets.
 The second phase of plant photosynthesis, also known as the Calvin-
Benson cycle, is a light-independent reaction that converts carbon dioxide
into glucose (fuel).
 The ‘Solar Water Splitting’ or ‘Photocatalytic Water Splitting’ is an artificial
photosynthesis process in which the reaction takes place in the presence of a
photocatalysis in a photoelectrochemical cell specifically used for the dissociation
of water into its constituent parts,Hydrogen (H2) and Oxygen (O2), using either
artificial or natural light.
14.7 KEY WORDS
 Solar energy: Solar energy is radiant light and heat from the Sun that is
harnessed using a range of ever-evolving technologies such as solar
heating, photovoltaics, solar thermal energy, solar architecture, molten salt
power plants and artificial photosynthesis.
 Solar cell: A solar cell, or photovoltaic cell, is an electrical device that
converts the energy of light directly into electricity by the photovoltaic effect,
which is a physical and chemical phenomenon.
 Dye-sensitized solar cell: A dye-sensitized solar cell is a low-cost solar
cell belonging to the group of thin film solar cells based on a semiconductor
formed between a photo-sensitized anode and an electrolyte, a photoelectro-
chemical system.
Self-Instructional
296 Material
 Artificial photosynthesis: Artificial photosynthesis is a chemical process Solar Energy
Conversion:
that bio-mimics the natural process of photosynthesis to convert sunlight, Basic Principles
water, and carbon dioxide into carbohydrates and oxygen.
 Hydrogen catalysts: Hydrogen is the simplest solar fuel to synthesize,
NOTES
since it involves only the transference of two electrons to two protons.
 Photoelectrochemical cells: Photoelectrochemical cells are defined as
a heterogeneous system that uses light for producing either electricity or
hydrogen.

EXERCISES

1. What is solar energy?
2. Brief a note on the two main types of solar energy technologies.
3. Write short note the followings:
i. Solar array
ii. Solar modules
iii. AC vs DC
4. Draw a well labelled diagram for p-n structure as an internal electric field
5. How are solar cells, solar modules, solar panels and solar arrays or systems
related to each other?
6. Brief a note on photoelectrochemical cells.
7. Give a brief overview of water oxidation and hydrogen evolution reaction.
1. Define the term solar energy. Explain solar energy conversion.
2. Explain with the help of diagram solar radiation in the electromagnetic
spectrum
3. Discuss about the factors determining the amount of solar energy generation.
4. Explain the principles of solar energy conversion.
5. Give a detailed note on solar panel and photovoltaic cell.
6. Explain in detail about dye-sensitized solar cell.
7. Elaborate a detailed note on artificial photosynthesis.
8. Explain solar water splitting and its methodology.
Self-Instructional
Material 297
Solar Energy
Conversion: 14.9 FURTHER READINGS
Basic Principles

NOTES New Age International (P) Ltd.
& Company Ltd.
Self-Instructional
298 Material
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BLOCK -I: SURFACE CHEMISTRY

BLOCK -II: PHOTOCHEMISTRYAND RADIATION CHEMISTRY

BLOCK -III: POLYMER CHEMISTRY

BLOCK -IV: COLLOIDS AND SOLAR ENERGY

BLOCK I: SURFACE CHEMISTRY

UNIT 2 SURFACE AREA REACTION 15-40

UNIT 3 SURFACE EXCESS 41-71

UNIT 5 ENERGY TRANSFER MECHANISMS 97-115

UNIT 6 FLASH PHOTOLYSIS 116-132

UNIT 7 RADIATION CHEMISTRY 133-154

BLOCK III: POLYMER CHEMISTRY

UNIT 9 STEPWISE POLYMERIZATION 172-189

UNIT 10 KINETICS AND MECHANISM POLYMERIZATION 190-206

BLOCK IV: COLLOIDS AND SOLAR ENERGY

UNIT 13 SOLAR ENERGY CONVERSION: POLYMERS AND POLYMERIZATION

Physical chemistry is the study of macroscopic, atomic, subatomic, and particulate

Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or

After going through this unit, you will be able to:

Fig. 1.1: Adsorption of a Gas on a Solid Surface

Adsorption of Gases by Solids

Fig. 1.2: Five Types of Adsorption Isotherms

p0 = Pressure required to condense the gas to liquid.

The Freundlich Adsorption Isotherm: To show the variation of the amount of

Fig. 1.3: Freundlich’s Adsorption Isotherm

at constant temperature and is known as the Langmuir adsorption isotherm. The

Fig. 1.4 Langmuir Adsorption Isotherm

This equation is similar to an equation for a straight line. Hence, if p/y is

Fig. 1.5 Isotherm Plot according to BET Equation

Fig. 1.6 Adsorption of Acetic Acid by Charcoal

This type of adsorption is also affected by temperature and concentration.

Fig. 1.7 Temkin Adsorption Isotherm.

adsorption of cadmium ion onto nanozero-valent iron particles follows a

Check Your Progress

1.5 KEY WORDS

 Adsorption: Adsorption is the adhesion of atoms, ions or molecules from

NOTES Short Answer Questions

1.7 FURTHER READINGS

Rohatgi-Mukherjee, K.K. 2008. Fundamentals of Photochemistry. New Delhi:

UNIT 2 SURFACE AREA REACTION

After going through this unit, you will be able to:

Fig. 2.1 Force acting on a molecule in a liquid

Fig. 2.2 Calculation of force on a liquid surface

Fig. 2.3 Capillary Rise Method for Measuring Surface Tension

the stalagmometer and consists of a bubbled capillary

Similarly, substituting the various values at 20°C (293.16 K)

Fig. 2.5: Identification of lattice planes by Miller indices

Fig. 2.6. The Octahedron with the Front Faces Indexed

Fig. 2.7 Elements of Symmetry of a Cube

Fig. 2.9 The Fourteen Bravaislattices

Fig. 2.10 Seven-Crystal Systems

Table 2.4: The crystal system

Packing of Atoms in Close-packed Structure

Fig. 2.11 Several ways of packing spheres

Check Your Progress

The rate of product formation is k2 A (where A is the surface coverage of

and I (i.e., kAPAN(1-I- A) = where k and k’

If the pressure of the reactant is low compared to that of the inhibitor, so

If, in addition, the inhibitor is very strongly adsorbed, then and

i.e., the apparent activation energy is , the true activation energy