CHE506 Physical Methods in Chemistry

YASHWANTRAO CHAVAN MAHARASHTRA OPEN UNIVERSITY
SCHOOL OF SCIENCES
(FORMERLY SCHOOL OF ARCHITECTURE, SCIENCE & TECHNOLOGY)
V154: M.Sc. Chemistry

2023 {As per NEP 2020}
Pattern
CHE506
PHYSICAL METHODS in
CHEMISTRY - I
(4 Credits)
Semester - I
Email: director.ast@ycmou.ac.in
Website: www.ycmou.ac.in
Phone: +91-253-2231473
CHE506
Yashwantrao Chavan Maharashtra
Physical Methods
Open University Nashik
In Chemistry
Brief Contents
Vice Chancellor’s Message ................................................................................................... 3
Foreword By The Director ................................................................................................... 4
Credit 01 .............................................................................................................................. 5
Credit 01 -Unit 01: UV-Visible Spectroscoy .................................................................... 6
Credit 01-Unit 02: IR Spectroscopy................................................................................ 35
Credit 01-Unit 03: Intrumentation and Application: bet ............................................... 61
Credit 01-Unit 04: Principles and Applications of XRD ................................................. 77
Credit 02 ............................................................................................................................ 99
Credit 02-Unit 01: Thermal Analysis ............................................................................. 100
Credit 02-Unit 02: Thermo Mechanical Analysis .......................................................... 139
Credit 02-Unit 03: Descriparion of ESCA Spectrometer ............................................... 175
Credit 02-Unit 04: Auger Electron Spectroscopy .......................................................... 194
Credit 03 ........................................................................................................................... 208

Credit 03-Unit 01: Diffraction Methods ........................................................................ 209
03-Unit 02: Raman Spectroscopy ................................................................................... 224
Credit 03-Unit 03: ESR Spectroscpoy Theory ............................................................... 248
Credit 03-Unit 04: Identification of Free Radicals ........................................................ 270
Credit 04 ........................................................................................................................... 280

Credit 04-Unit 01: Atomic Absorption Spectroscopy ..................................................... 281
Credit 04-Unit 02: Plasma Sources & Applications of Flame Emission Spectrometry .. 304
Credit 04-Unit 03: Intrumentation & Interference Applications of AAS ...................... 331
Credit 04-Unit 04: Inductively Coupled Plasma Spectroscopy: .................................... 349
Feedback Sheet for the Student ........................................................................................ 370
CHE506: Physical Methods In Chemistry Page 1

CHE506: Physical Methods In Chemistry
Yashwantrao Chavan Maharashtra Open University
Vice-Chancellor: Prof.Dr. P.G.Patil
School of Architecture, Science and Technology
Director of the School: Dr. Sunanda More
Programme Advisory Committee
Dr Sunanda More Dr. ChetanaKamlaskar
Director, Assistant Professor, School of Architecture,
School of Architecture, Science & Technology, Science & Technology, YCMOU, Nashik
YCMOU, Nashik
Prof. Dr. S. D. Delekar, Prof. Dr. Nandkishor N. Karade, Dr. ArvindVinayakNagawade
Professor, Deptt of Chemistry,
Deptt of Chemistry, Vice Principal& Head Deptt of
Shivaji University
Kolhapur - 416004 RashtrasantTukadojiMaharaj Chemistry, Ahmednagar College
Nagpur University, Ahmednagar,
Nagpur 440033 Dist: Ahmednagar, 414001
Dr. Tukaram. S. Thopate, Prof. ShamraoGolekar Associate Dr. Borhade Ashok Vishram
Vice Principal and Head Deptt
Professor and Head Deptt of Associate Prof., Deptt of
of Chemistry, New Arts,
Commerce Science College, Chemistry Jamkhed College
Chemistry, H.P.T. Arts & R.Y.K.
Parner, TalukaParner, Dist: Jamkhed,
Ahmednagar 414302 Dist: Ahmednagar 413201 Science College, Nashik 422001
Dr. AmolKategaonkar Dr. Bharat More

Associate Prof. in Chemistry,
Academic Coordinator, School of
KSKW College, Cidco,
Architecture, Science and Technology,
Nashik 422008
YCMOU, Nashik-422 222
Development Team
Instructional Course Coordinators Book Writer Book Editor
Technology Editor
Dr Sunanda More 1.Dr. Bharat More Dr. Bharat P. More Prof. Dr. Ashok V.
Director, Academic Coordinator, Borhade
2.Mr.Ghanshyam Patil
School of Architecture, School of Architecture, Department Of
Science & Technology, Academic Coordinator, Science & Technology, Chemistry,H.P.T. ARTS
YCMOU, Nashik School of YCMOU, Nashik- & R.Y.K. Science
AST,YCMOU, Nashik- 422222 College Nashik-422001
422 222
This work by YCMOU is licensed under a Creative Commons Attribution-Non

Commercial-ShareAlike 4.0 International License .
 Book Publication : 31-October-2022 Publication No:2561

 Publisher : Dr. Prakash Deshmukh [I/C], Registrar, YCMOU, Nashik- 422 222
 ISBN: 978-93-95855-07-5
 This SLM V142: M.Sc. Chemistry {2022 Pattern}, dtd. 31/10/2022
Book used in V154: M.Sc. Chemistry {2023 Pattern}, dtd. 31/08/2023

V ICE C HANCELLOR ’ S M ESSAGE
Dear Students,
Greetings!!!
I offer cordial welcome to all of you for the Master’s degree programme of Yashwantrao
Chavan Maharashtra Open University.
As a post graduate student, you must have autonomy to learn, have information and knowledge
regarding different dimensions in the field of Chemistry and at the same time intellectual development is
necessary for application of knowledge wisely. The process of learning includes appropriate thinking,
understanding important points, describing these points on the basis of experience and observation,
explaining them to others by speaking or writing about them. The science of Education today accepts
the principle that it is possible to achieve excellence and knowledge in this regard.
The syllabus of this course has been structured in this book in such a way, to give you autonomy to
study easily without stirring from home. During the counseling sessions, scheduled at your respective study
centre, all your doubts will be clarified about the course and you will get guidance from some qualified
and experienced counsellors/ professors. This guidance will not only be based on lectures, but it will also
include various techniques such as question-answers, doubt clarification. We expect your active
participation in the contact sessions at the study centre. Our emphasis is on ‘self study’. If a student
learns how to study, he will become independent in learning throughout life. This course book has been
written with the objective of helping in self-study and giving you autonomy to learn at your convenience.
During this academic year, you have to give assignments, complete laboratory activities, field visits
and the Project work wherever required. You have to opt for specialization as per programme structure.
You will get experience and joy in personally doing above activities. This will enable you to assess
your own progress and thereby achieve a larger educational objective.
We wish that you will enjoy the courses of Yashwantrao Chavan Maharashtra Open University,
emerge successful and very soon become a knowledgeable and honorable Master’s degree holder of
this university.
I congratulate “Development Team” for the development of this excellent high quality “Self-
Learning Material (SLM)” for the students. I hope and believe that this SLM will be immensely useful
for all students of this program.
Best Wishes!
- Prof. Dr. P. G. Patil
Vice-Chancellor, YCMOU

F OREWORD B Y T HE D IRECTOR
Dear Students,
Greetings!!!
This book aims at acquainting the students with conceptual and applied fundamentals about
Chemistry required at degree level.
The book has been specially designed for Science students. It has a comprehensive
coverage of concepts and its application of Chemistry in practical life. The book contains
numerous examples to build understanding and skills.
The book is written with self- instructional format. Each chapter is prepared with
articulated structure to make the contents not only easy to understand but also interesting to
learn.
Each chapter begins with learning objectives which are stated using Action Verbs as per
the Bloom’s Taxonomy. Each Unit is started with introduction to arouse or stimulate
curiosity of learner about the content/ topic. Thereafter the unit contains explanation of
concepts supported by tables, figures, exhibits and solved illustrations wherever necessary
for better effectiveness and understanding.
This book is written in simple language, using spoken style and short sentences. Topics of
each unit of the book presents from simple to complex in logical sequence. This book is
appropriate for low achiever students with lower intellectual capacity and covers the
syllabus of the course.
Exercises given in the chapter include conceptual questions and practical ques tions so as to
create a ladder in the minds of students to grasp each and every aspect of a particular
concept.
I thank the students who have been a constant motivation for us. I am grateful to the
writers, editors and the School faculty associated in this SLM development of the Program
me.
Best Wishes to all of you!!!
- Dr. Sunanda More

Director,
School of Arch., Science &Technology,
YCMOU

C REDIT 01

CREDIT 01 -UNIT 01: UV-VISIBLE SPECTROSCOY
LEARNING OBJECTIVES
After successful completion of this unit, you will be able to
 Explain the advanced UV-visible spectroscopy.
 Uunderstand the origin of electromagnetic radiation.
 Predict the number of fundamental modes of vibration of a molecule.
INTRODUCTION
Introduction UV spectroscopy is type of absorption spectroscopy in which light of ultra -

violet region (200-400 nm.) is absorbed by the molecule. Absorption of the ultra -violet
radiations results in the excitation of the electrons from the ground state to h igher energy
state. The energy of the ultra-violet radiation that are absorbed is equal to the energy
difference between the ground state and higher energy states. Generally, the most favoured
transition is from the highest occupied molecular orbital (HOMO ) to lowest unoccupied
molecular orbital (LUMO). For most of the molecules, the lowest energy occupied
molecular orbitals are s orbital, which correspond to sigma bonds. The p orbitals are at
somewhat higher energy levels, the orbitals (nonbonding orbitals ) with unshared paired of
electrons lie at higher energy levels. The unoccupied or antibonding * orbitals ( and σ* )
are the highest energy occupied orbitals. In all the compounds (other than alkanes), the
electrons undergo various transitions. Some of the important transitions with * increasing
energies are: nonbonding to , nonbonding to σ* *  to , *, σ to and σ to σ*

01-01-01: PRINCIPLE OF UV SPECTROSCOPYS
The Principle of UV-Visible Spectroscopy is based on the absorption of ultraviolet light or
visible light by chemical compounds, which results in the production of distinct spectra.
Spectroscopy is based on the interaction between light and matter. When the matter absorbs
the light, it undergoes excitation and de-excitation, resulting in the production of a
spectrum. When matter absorbs ultraviolet radiation, the electrons present in it und ergo
excitation. This causes them to jump from a ground state (an energy state with a relatively
small amount of energy associated with it) to an excited state (an energy state with a
relatively large amount of energy associated with it). It is important t o note that the
difference in the energies of the ground state and the excited state of the electron is always
equal to the amount of ultraviolet radiation or visible radiation absorbed by it.
INSTRUMETATION AND WORKING OF UV SPECTROSCOPY
Instruments for measuring the absorption of U.V. or visible radiation are made up of the
following components;
1. Sources (UV and visible)
2. filter or monochromator
3. Sample containers or sample cells
4. Detector
1. Radiation source:
It is important that the power of the radiation source does not change abruptly
over its wavelength range. The electrical excitation of deuterium or hydrogen at low
pressure produces a continuous UV spectrum. The mechanism for this involves
formation of an excited molecular species, which breaks up to give two atomic
species and an ultraviolet photon Both Deuterium and Hydrogen lamps emit
radiation in the range 160 - 375 nm. Quartz windows must be used in these lamps,

and quartz cuvettes must be used, because glass absorbs radiation of wavelengths
less than 350 nm.
Various UV radiation sources are as follows
a. Deuterium lamp
b. Hydrogen lamp
c. Tungsten lamp
d. Xenon discharge lamp
e. Mercury arc lamp
Various Visible radiation sources are as follows
a. Tungsten lamp
b. Mercury vapour lamp
c. Carbonone lamp
2. filters or monochromators:
All monochromators contain the following component parts;
• An entrance slit
• A collimating lens
• A dispersing device (a prism or a grating)
• A focusing lens
• An exit slit
Polychromatic radiation (radiation of more than one wavelength) e nters the

monochromator through the entrance slit. The beam is collimated, and then strikes the
dispersing element at an angle. The beam is split into its component wavelengths by the
grating or prism. By moving the dispersing element or the exit slit, rad iation of only a
particular wavelength leaves the monochromator through the exit slit.
3. sample containers or sample cells:
A variety of sample cells available for UV region. The choice of sample cell is based on
a) the path length, shape, size
b) the transmission characteristics at the desired wavelength

c) the relative expense
The cell holding the sample should be transparent to the wavelength region to be recorded.
Quartz or fused silica cuvettes are required for spectroscopy in the UV region. Silicate

glasses can be used for the manufacture of cuvettes for use between 350 and 2000 nm. The
thickness of the cell is generally 1 cm. cells may be rectangular in shape or cylindrical with
flat ends.
4. Detectors:
In order to detect radiation, three types of photos ensitive devices are
a. photovoltaic cells or barrier- layer cell
b. phototubes or photoemissive tubes
c. photomultiplier tubes
Photovoltaic cell is also known as barrier layer or photronic cell. It consists of a metallic
base plate like iron or aluminium which act s as one electrode. On its surface, a thin layer of
a semiconductor metal like selenium is deposited. Then the surface of selenium is covered
by a very thin layer of silver or gold which acts as a second collector tube.
When the radiation is incident upon the surface of selenium, electrons are generated at the
selenium- silver surface and the electrons are collected by the silver. This accumulation at
the silver surface creates an electric voltage difference between the silver surface and the
basis of the cell.
Phototubes are also known as photo emissive cells. A phototube consists of an evacuated
glass bulb. There is light sensitive cathode inside it. The inner surface of cathode is coated
with light sensitive layer such as potassium oxide and silver oxide.
When radiation is incident upon a cathode, photoelectrons are emitted. These are collected
by an anode. Then these are returned via external circuit. And by this process current is
amplified and recorded.
The photomultiplier tube is a commonly used detect or in UV spectroscopy. It consists of a
photo emissive cathode (a cathode which emits electrons when struck by photons of
radiation), several dynodes (which emit several electrons for each electron striking them)
and an anode.
A photon of radiation entering the tube strikes the cathode, causing the emission of several
electrons. These electrons are accelerated towards the first dynode (which is 90V more
positive than the cathode). The electrons strike the first dynode, causing the emission of
several electrons for each incident electron. These electrons are then accelerated towards
the second dynode, to produce more electrons which are accelerated towards dynode three
and so on. Eventually, the electrons are collected at the anode. By this time, each origina l
photon has produced 106 - 107 electrons. The resulting current is amplified and measured.
Photomultipliers are very sensitive to UV and visible radiation. They have fast response
times. Intense light damages photomultipliers; they are limited to measurin g low power
radiation.

Single Beam Spectrophotometer:
Single beam spectrophotometer is an analytical instrument in which all the light waves
coming from the light source passes through the sample. Therefore, the measurements are
taken as the intensity of light before and after the light pass through the sample. These
single beam spectrophotometers are more compact and optically simpler than double beam
spectrophotometers. And also these instruments are less expensive.

The sensitivity of detection of the light beam after it passes through the sample is high
since it uses a non-split light beam (therefore, high energy exists throughout). Single beam
spectrophotometers are available in analysis at visible and ultraviolet wavelength ranges.
A single beam spectrophotometer measures the concentration of an analyte in a sample by
measuring the amount of light absorbed by that analyte. Here, the Beer Lambert Law comes
into operation. This law states that the concentration of an analyte is directly proporti onal
to the absorbance.
Double Beam Spectrophotometer:
Double beam spectrophotometer is an analytical instrument in which the light beam
coming from the light source splits into two fractions. One fraction acts as the reference
(the reference beam) while the other fraction passes through the sample (sample beam). As
a result, the reference beam does not pass through the sample.

The Pathway of Light Beam in a Double Beam Spectrophotometer The sample beam can
measure the absorbance of the sample. The re ference beam can measure the absorption (the
sample beam can be compared with the reference beam). Therefore, the absorption is the
ratio between the sample beam (after passing through the sample) and a reference beam. A
spectrophotometer has a monochromator that isolates the desired wavelengths from a light
beam. The reference beam and sample beam recombine before moving to the
monochromator. Consequently, this avoids or compensate the electronic and mechanical
effects on both sample and reference beams, e qually.
What is the Difference Between Single Beam and Double Beam Spectrophotometer?
Single Beam vs Double Beam Spectrophotometer Single beam spectrophotometer is an
analytical instrument in which all the light waves coming from the light source passes
through the sample. Double beam spectrophotometer is an analytical instrument in which
the light beam coming from the light source splits into two fractions
Light Beam Single beam spectrophotometer uses a non -split light beam. Double beam
spectrophotometer uses a light beam that is split into two fractions before passing through
the sample.
Measurement The measurements taken from single beam spectrophotometers are less
reproducible because a single light beam is used. The measurements taken from double
beam spectrophotometers are highly reproducible because electronic and mechanical effects
on both sample and reference beams are equal.
Summary – Single Beam vs Double Beam Spectrophotometer:
A spectrophotometer is an instrument that analyses the components of a solution by
observing the capability to absorb light. There are two main types of spectrophotometers;
single beam and double beam spectrophotometer. The difference between single beam and
double beam spectrophotometer is that, in single beam spectrophotom eter, all the light
waves pass through the sample whereas, in double beam spectrophotometer, the light beam
splits into two parts and only one part passes through the sample.
01-01-02 CONJUGATED DIENE CORRELATIONS:
Conjugated dienes and polyenes are found in most organic compounds. For
example, even a benzene ring is a conjugated polyene. Therefore it is useful to know how to
utilize the Woodward-Fieser rules to calculate the wavelength of maximum absorption of
conjugated dienes and polyenes.
According to Woodward’s rules the λmax of the molecule can be calculated using a
formula:
λmax = Base value + Σ Substituent Contributions + Σ Other Contributions
Here the base value depends upon whether the diene is a linear or heteroannular or transoid
diene, or whether it is a cyclic or homoannular diene (each of these will be explained in

greater detail below). The sum of all substituent contributions are added to the base value to
obtain the wavelength of maximum absorption of the molecule.
1. In example 1, the double bond present within ring A is exocyclic to ring B as it

is attached to an atom which is shared between ring A and ring B, while the
double bond present in ring B is not connected to any ring A atoms and is within
just one ring, hence making it endocyclic.
2. In example 2, both double bonds are present within ring B with connections to
shared carbon atoms with ring A, making both the double bonds exocyclic.
3. In example 3, there is a single double bond which is exocyclic at two points to
two different rings. In such a case, the influence would be 2 times + 5 nm (i.e +
10 nm).
Each type of diene or triene system is having a certain fixed value at which
absorption takes place; this constitutes the Base value or Parent value. The
contribution made by various alkyl substituents or ring residue, double bond
extending conjugation and polar groups such as –Cl, -Br etc are added to the basic
value to obtain λmax for a particular compound.
a) Homoannular Diene:- Cyclic diene having conjugated double bonds in same
ring.
b) Heteroannular Diene:- Cyclic diene having conjugated double bonds in different
rings.
c) Endocyclic double bond:- Double bond present in a ring.

d) Exocyclic double bond: - Double bond in which one of the doubly bonded atoms
is a part of a ring system.
Here Ring A has one exocyclic and endocyclic double bond. Ring B has only one
endocyclic double bond.
PARENT VALUES AND INCREMENTS FOR DIFFERENT SUBSTITUENTS/ GROUPS:
I) CONJUGATED DIENE CORRELATIONS:
i) Base value for homoannular diene = 253 nm
ii) Base value for heteroannular diene = 214 nm
iii) Alkyl substituent or Ring residue attached to the parent diene = 5 nm
iv) Double bond extending conjugation = 30 nm
v) Exocyclic double bonds = 5 nm
vi) Polar groups: a) -OAc = 0 nm
vii) -OAlkyl = 6 nm
viii) -Cl, -Br = 5 nm
Eg:
Exocyclic double bond = 1 x 5 = 5 nm

λmax = 214 + 15 + 5 = 234 nm
II) α, β UNSATURATED CARBONYL COMPOUNDS OR KETONES:
1. Base value: a) Acyclic α, β unsaturated ketones = 214 nm
b) 6 membered cyclic α, β unsaturated ketones = 215 nm
c) 5 membered cyclic α, β unsaturated ketones = 202 nm
d) α, β unsaturated aldehydes = 210 nm
e) α, β unsaturated carboxylic acids & esters = 195 nm
2. Alkyl substituent or Ring residue in α position = 10 nm
3. Alkyl substituent or Ring residue in β position = 12 nm
4. Alkyl substituent or Ring residue in γ and higher positions = 18 nm
5. Double bond extending conjugation = 30 nm

6. Exocyclic double bonds = 5 nm
7. Homodiene compound = 39 nm
8. Polar groups: a) –OH in α position = 35 nm
–OH in β position = 30 nm
–OH in δ position = 50 nm
b) –OAc in α, β, γ, δ positions = 6 nm
c) –OMe in α position = 35 nm
–OMe in β position = 30 nm
–OMe in γ position = 17 nm
–OMe in δ position = 31 nm
d) –Cl in α position = 15 nm
–Cl in β position = 12 nm
e) –Br in α position = 25 nm
–Br in β position = 30 nm
f) –NR2 in β position = 95 nm
Eg:
Base value =246 nm

Ring residue in o- position = 1 x 3 = 3 nm
Polar group -OCH3 in p- position = 25 nm
λmax = 274 nm

Concept of Chromophore and Auxochrome in the UV spectroscopy:
Chromophore- Chromophore is defined as any isolated covalently bonded group that
shows a characteristic absorption in the ultraviolet or visible region (200 -800 nm).
Chromophores can be divided into two groups
a) Chromophores which contain p electrons and which undergo pie to pie* transitions.
Ethylenes and acetylenes are the example of such chromophores.

b) Chromophores which contain both p and nonbonding electrons. They undergo two
types of transitions; pie to pie* and nonbonding to pie* . Carbonyl, nitriles, azo
compounds, nitro compounds etc. are the example of such chromophores.
Auxochromes- An auxochrome can be defined as any group which does not itself act
as a chromophore but whose presence brings about a shift of the absorption band
towards the longer wavelength of the spectrum. –OH,-OR,-NH2,-NHR, -SH etc. are the
examples of auxochromic groups.
Absorption and intensity shifts in the UV spectroscopy:
There are four types of shifts observed in the UV spectroscopy
a) Bathochromic effect- This type of shift is also known as red shift. Bathochromic
shift is an effect by virtue of which the absorption maximum is shifted towards the longer
wavelength due to the presence of an auxochrome or change in solvents. The nonbonding to
pie* transition of carbonyl compounds observes bathochromic or red shift.
b) Hypsochromic shift- This effect is also known as blue shift. Hypsochromic
shift is an effect by virtue of which absorption maximum is shifted towards the
shorter wavelength. Generally it is caused due to the removal of conjugation or
by changing the polarity of the solvents.
c) Hyperchromic effect- Hyperchromic shift is an effect by virtue of which
absorption maximum increases. The introduction of an auxoc hrome in the
compound generally results in the hyperchromic effect.
d) Hypochromic effect- Hyperchromic effect is defined as the effect by virtue of
intensity of absorption maximum decreases. Hyperchromic effect occurs due to
the distortion of the geometry of the molecule with an introduction of new
group.
STERIC EFFECTS
Steric hindrance will also affect the influence of an auxochrome on a chromophore.
Electron systems conjugate best when the molecule is planar in conjugation. In the presence
of an auxochrome prevents the molecule from being planar than large effects will be
noticed in the spectrum.eg. m and p-methyl groups in the diphenyls have predictable but
slight effects on the spectra compared with that of diphenyl itself.
Cis and Trans isomers of linear polyenes also show difference in their spectra.
The all trans isomer has the longer conjugated system λmax is at a longer wavelength and
Emax is higher than for all cis or mixed isomer.
ULTRAVIOLET (UV) & VISIBLE SPECTROSCOPY:
 Ultraviolet and visible spectroscopy also known as electronic spectroscopy is used
to measure the number of conjugation of double bond and aromatic conjugation
within the molecule.

 It involves the promotion of electrons from HOMO to LUMO (HOMO means
Highest Occupied Molecular Orbital whereas LUMO means Lowest Unoccupied
Molecular Orbital).
 The HOMO-LUMO gap decrease as the conjugation increase.
 The ultraviolet region corresponds to 400-200 nm and visible region to 800- 400
nm.
 UV-visible spectroscopy based on Beer-Lambert law.
log Io I ⁄ = ε. 𝑙. 𝑐or ϵ = 𝐴/𝑐
Where,
Io = intensity of incident light
I = intensity of transmitted light
ε = molar absorptivity
l = path length of sample
c = concentration of sample
A = Absorbance
 Absorbance (A): It is reciprocal of Transmittance
Absobance (A) = Optical density (D) = log 1 T or log Io I
 Transmittance (T): The fraction of incident light transmitted is known as
Transmittance.
Transmittance (T) = I / Io
SOLVED PROBLEMS 01
1) Guanosine has a maximum absorbance at 275 nm. ε275 = 8400 M-1 Cm-1 and the path
length is 1 cm. Using a spectrophotometer, you find the that A275 = 0.7 . What is the
concentration of guanosine?
a) Solution : A = εcl
2) There is a substance in a solution (4 moles/liter). The length of cuvette is 2 cm and

only 50% of the certain light beam is transmitted. What is the absorption coefficient of the
substance?

Solution:
SHORT ANSWER QUESTIONS WITH MODEL ANSWER 01

1) Explain the effect of polar solvent on 𝜋 − 𝜋 * transition.
Ans- In polar solvent, 𝜋 − 𝜋 * transitions shift towards longer wavelength (Red
shift), because dipole interactions with polar solvent molecules lower the energy of
excited state (𝜋 * ) than that of the ground state (𝜋 * orbital’s are stabilized by
hydrogen bonding with polar solvent).
2) Explain the effect of polar solvent on 𝑛 − 𝜋 * transition.
Ans- Whereas in polar solvent, 𝑛 − 𝜋 * transitions shift towards lower wavelength (Blue
shift), because dipole interactions with polar solvent molecules lower the energy of ground
state (𝑛) than that of the excited state (𝑛 orbital’s are stabilized by hydrogen bonding with
polar solvent).
3) What is UV-Visible Spectroscopy ?
4) What is the result of interaction of UV-Vis light and the molecule?
01-01-02: ELECTRONIC TRANSITIONS:

When molecule is getting excited by the absorption of electromagnetic radiation in UV-
visible region then its electrons are promoted from ground state to excited state or from
bonding orbital to anti-bonding orbital.
Types of electronic transitions
a) 𝜎 − 𝜎 * Transition: transition of an electron from bonding sigma orbital ( 𝜎) to anti-
bonding sigma orbital (𝜎* ), is represented by 𝜎 − 𝜎 * transition. For example, alkanes
because in alkane all the atoms are held together with sigma bond.
b) 𝑛 − 𝜎 * &𝑛 − 𝜋 * Transition: Transitions from non-bonding molecular (𝑛) orbital to
anti-bonding sigma orbital or anti-bonding pi orbital (𝜋* ), are represented by 𝑛 − 𝜎 * or 𝑛
− 𝜋 * transition respectively. These transition required less energy than 𝜎 − 𝜎 * transition.
For example, alkyl halide, aldehydes, ketones etc.
c) 𝜋 − 𝜋 * Transition: This type of transition generally show in unsaturated molecules like
alkenes, alkynes, aromatics, carbonyl compounds etc. This transition required less
energy as compare to 𝑛 − 𝜎 * transition.

Absorption, intensity shift & UV spectrum:
a) Bathochromic shift: It is also known as Red shift, in this case absorption shift
towards longer wavelength (𝜆max).
b) Hypsochromic shift: It is also known as Blue shift, in this case absorption shift
towards shorter wavelength (𝜆max).
c) Hyperchromic shift: Intensity of absorption maximum ( 𝜀max) increases.
d) Hypochromic shift: Intensity of absorption maximum ( 𝜀max) decrease.

Chromophores & Auxochromes:
a) Chromophores: Chromophore is a covalently unsaturated group absorbed
electromagnetic radiation in UV-visible region and impart color to the compound. For
example, C=C, C≡C, benzene, NO2 etc.

b) Auxochromes: Auxochrome is a saturated group (containing lone pair of electron), when
auxochrome attach to the Chromophore absorption shift towards longer wavelength. For
example, -OH, -SH, -NH etc.
Factor affecting absorbance & intensity:

a) Conjugation:
Absorption shift towards longer wavelength, if double bonds (chromophore) present in the
molecule are in conjugation. For example,
In compound ‘A’, double bonds are in conjugation therefore ‘A’ possessing higher
wavelength (𝜆max) as compare to compound ‘B’ (non -conjugated derivative).
We know that,
As the conjugation increase transition energy (E) between the orbitals is decrease and
therefore wavelength (𝜆max) increase.
b) Effect of solvent: In polar solvent, 𝜋 − 𝜋 * transitions shift towards longer

wavelength (Red shift), because dipole interactions with polar solvent molecules lower
the energy of excited state (𝜋* ) than that of the ground state (𝜋 * orbital’s are stabilized
by hydrogen bonding with polar solvent).

Whereas in polar solvent, 𝑛 − 𝜋 * transitions shift towards lower wavelength (Blue shift),
because dipole interactions with polar solvent molecules lower the energy of ground state
(𝑛) than that of the excited state (𝑛 orbital’s are stabilized by hydrogen bonding with polar
solvent).

SOLVED PROBLEMS 02
3) It was found tha t an unknown path length of 4.00 cm was required to match the
intensity of a 2.00cm path length of a 0.05 M standard. the concentration of the
unknown would be
×0.05M =0.025M
4) An absorbance 0.36 obtained after 11.5 ml of titrating agent was added to 68.0 ml
of an initial solution.what was the corrected absorbance of the solution? What would the
% error have been if the correction was not made ?
Solution: Corrected absorbance= × 0 436 = 0 510
%𝑒𝑟𝑟𝑜𝑟 = × 100 = × 100 = 14 5%
SHORT ANSWER QUESTIONSWITH MODEL ANSWER 02

5) What is Chromophore? How does it differ from auxochrome?
a) Chromophores: Chromophore is a covalently unsaturated group absorbed
electromagnetic radiation in UV-visible region and impart color to the compound.
For example, C=C, C≡C, benzene, NO2 etc. b) Auxochromes: Auxochrome is a
saturated group (containing lone pair of electron), when auxochrome attach to the
Chromophore absorption shift towards longer wavelength. For example, -OH, -SH, -
NH etc.

6) Explain the term Hypsochromic shift and Bathochromic shift.
a) Bathochromic shift: It is also known as Red shift, in this ca se absorption shift
towards longer wavelength (𝜆max). b) Hypsochromic shift: It is also known as
Blue shift, in this case absorption shift towards shorter wavelength ( 𝜆max).
7) Write the short note on electronic transitions.
8) What is electronic spectroscopy?
01-01-03: THE WOODWARD-FIESER RULES (CALCULATION OF 𝝀MAX (NM)

IN CONJUGATED DIENES )

The Woodward-Fieser rules (Calculation of 𝝀 max (nm) in α,β-unsaturated carbonyl
compounds):

SOLVED P ROBLEMS 03
5) The λ of 𝝈 to 𝝈 * transitions lies in the
(a) IR region
(b) Visible region
(c ) UV region
(d) None of the above
Answer: (c ) The λ of 𝝈 to 𝝈 * transitions lies in the UV region.
6) What is the wavelength range of the UV spectrum?
(a) 100 nm to 500 nm
(b) 200 nm to 800 nm
(c ) 300 nm to 1000 nm
(d) 400 nm to 1600 nm
9) What kinds of detectors are used in UV-Visible spectroscopy?
A widely used detector in UV-Vis spectroscopy is the Photomultiplier tube. It consists of a
photo emissive cathode (which is a cathode that releases electrons when it is hit by radiation
photons), multiple dynodes (which is a device that emit multiple electrons for each striking
electron), and an anode.
10) What is beer lambert law?
Answer: The beer lambert law states that there is a linear connection between the absorbance
and the concentration of the solution. The intensity of the beam of monochromatic radiation
decreases exponentially with an increase in the thickness x and the concentration c of the
absorbing medium.
A = log (I° / I) = εLc Here,
A = Absorbance
I° = Intensity of the incident beam,
I = Intensity absorbed by the sample
ε = Molar Extinction Coefficient
L = Distance covered by the light through the solution
c = Concentration of the absorbing species
11) Write the applications of UV-Visible spectroscopy.
12) How does delocalisation of electron helped in getting a molecule to absorb UV-Visible
radiation and displaying the UV-Visible absorption spectra?

01-01-04: APPLICATION OF UV SPECTROSCOPY:
i) Extent of conjugation: As the double bond increase, absorption shift towards
longer wavelength.
ii) Distinction between conjugated and non conjugated compounds:
Both the above compound A & B are isomer of each other. Due to 𝑛 − 𝜋 *
transition, compound A appear at longer wavelength than compound B.
iii) Study of geometric isomerism:
In isomer A, due to steric hindrance, absorption shift towards lower wavelength.

We know that, steric hindrance destabilize the compound means ene rgy of the
molecule increase which decreases the wavelength.
iv) Used in the detection of impurities: Due to presence of impurities in the
compound, give additional peaks are observed in UV spectrum.
v) UV absorption spectroscopy can be used for the quantitativ e determination of
compounds that absorb UV radiation.
vi) UV absorption spectroscopy can characterize those types of compounds which
absorbs UV radiation thus used in qualitative determination of compounds.
Identification is done by comparing the absorption s pectrum with the spectra of
known compounds.
vii) This technique is used to detect the presence or absence of functional group in
the compound. Absence of a band at particular wavelength regarded as an
evidence for absence of particular group.
viii) Kinetics of reaction can also be studied using UV spectroscopy. The UV radiation
is passed through the reaction cell and the absorbance changes can be observed

ix) Many drugs are either in the form of raw material or in the form of formulation.
They can be assayed by making a suitable solution of the drug in a solvent and
measuring the absorbance at specific wavelength.
x) Molecular weights of compounds can be measured spectrophotometrically by

preparing the suitable derivatives of these compounds.
xi) UV spectrophotometer may be used as a detector for HPLC
xii) Other applications include the following: In clinical chemistry UV-visible

spectroscopy is used extensively in the study of enzyme kinetics. Enzymes cannot
be studied directly but their activity can be studied by analysing the speed of the
reactions which they catalyse. Reagents or labels can also be attached to
molecules to permit indirect detection and measurement of enzyme activity. The
widest use in the field of clinical diagnostics is as an indicator of tissue damage.
When cells are damaged by disease, enzymes leak into the bloodstream and the
amount present indicates the severity of the tissue damage. The relative
proportions of different enzymes can be used to diagnose disease, say of the liver,
pancreas or other organs which otherwise exhibit similar symptoms.
xiii) UV-visible spectroscopy is used for dissolution testing of tablets and products in
the pharmaceutical industry. Dissolution is a characterisation test commonly used
by the pharmaceutical industry to guide formulation desi gn and control product
quality. It is also the only test that measures the rate of in -vitro drug release as a
function of time, which can reflect either reproducibility of the product
manufacturing process or, in limited cases, in -vivo drug release.
xiv) In the biochemical and genetic fields UV-visible spectroscopy is used in the
quantification of DNA and protein/enzyme activity as well as the thermal
denaturation of DNA.
xv) In the dye, ink and paint industries UV-visible spectroscopy is used in the quality
control in the development and production of dyeing reagents, inks and paints
and the analysis of intermediate dyeing reagents.
xvi) In environmental and agricultural fields the quantification of organic materials
and heavy metals in fresh water can be carried out usi ng UV-visible spectroscopy.
CONCLUSION
In this lesson, we pointed out
1) Instrumentation of UV visible spectroscopy.
2) Woodward-Fieser and Scott rules
3) Concept of chromophore
4) Steric effects

END LESSON ACTIVITY
1. Describe the Instrumentation of UV visible spectroscopy.
2. State and explain the woodward-fieser rule
3. Explain the effect of steric effect in aromaticity.
4. What is electronic spectroscopy?
5. What is Chromophore? How does it differ from auxochrome?
6. Discuss how conjugation affects the intensity of absorption band.
7. Write the short note on electronic transitions.
8. Write notes on application of UV-visible spectroscopy.
9. Explain the term Hypsochromic shift and Bathochromic shift. What structural
features may lead to these shifts in organic molec ules?
10. Explain the effect of polar solvent on 𝜋 − 𝜋 * and 𝑛 − 𝜋 * transition.
11. How 1,3-pentadiene and 1,4-pentadiene can be distinguished by UV spectroscopy?
12. Why aniline behaves like that of benzene in acidic medium?
13. .Two isomeric dienes ‘A’ and ‘B’ having the molecular formula C5H8 absorb at 𝜆max
225 nm and 𝜆max 180 nm respectively. Write the structure of the two isomers.
14. Find out the 𝜆max of following molecules.
SOLVED PROBLEMS 04
7)

8)
a) Solution: Soln: Here two double bonds extend the configuration of the homoannular
diene system of the middle ring. There are five carbon substituents and three
exocyclic double bonds. The carbon indicated by an arrow is also a substituent on
two different double bonds and hence counted twice Thus  max = 253 + 2 × 30 + 5
× 5 + 3 × 5 = 253 + 60 + 25 + 15 = 353 n m.
13) What is the effect of solvent on the absorption of UV visible spectroscopy?
Answer: Solvent plays an important role in absorbing UV visible spectra. Solvent molecules
may form an electrostatic bond with the solute molecule. Thus, obscuring the excitation
energy of the solute molecule, thereby affecting the absorption peak.
A transparent dilute solution is generally preferred as a solvent in UV visible spectroscopy.
14) WHAT ARE THE APPLICATIONS OF UV-VISIBLE SPECTROSCOPY?

UV-Visible spectroscopy is widely used in the field of analytical chemistry, especially
during the quantitative analysis of a specific analyte. For example, the quantitative
analysis of transition metal ions can be achieved with the help of UV-Visible
spectroscopy. Furthermore, the quantitative analysis of conjugated organic compounds
can also be done with the help of UV-Visible spectroscopy. It can also be noted that this
type of spectroscopy can also be carried out on solid and gaseous analytes in some
conditions.
15) Explain the effect of polar solvent on 𝜋 − 𝜋 * and 𝑛 − 𝜋 * transition.
16) Discuss how conjugation affects the intensity of absorption band.
CHECK POINT
1) Radiation source for visible radiation is
a) Tungsten lamp
b) Nearnst glower
c) Hydrogen lamp d) None of these
2) Which of the following used as wavelength selector in spectroscopy
a) Prism
b) Diffraction grating
c) Both a and b
d) None of these
3) Photon detector used in Infra red region

a) Thermocouple
b) Photographic plate
c) Photomultiplier tube
d) Human eye
4) The internal energy of a molecule is its
a) rotational energy
b) vibrational energy
c) translational energy
d) all of these
SUMMARY
• Spectroscopy is the study of interaction of electromagnetic radiations with the matter and
is used to identify a substance, which may include UV, IR, NMR and Raman etc.
• The arrangement of all types of radiations in order of their increasing wavelength or
decreasing frequencies is known as electromagnetic spectrum.
• The absorption of energy can bring about trans lational, electronic, rotational or
vibrational motion or ionization of the molecules depending upon the frequency of the
electromagnetic radiation they receive.
• Spectrophotometer is an instrument, which measures the transmittance or absorbance of a
sample as a function of wavelength, when light of certain intensity and frequency range is
passed through the sample.
• Although, there are six possible transitions σ to σ ∗, π to σ∗, π to π∗, π to σ∗, n to π∗ and n
to σ, the most commonly observed transitions in organic molecules are π to π∗, n to σ∗ and
n to π∗.
KEY WORDS
Wavelength, Frequency, extensively conjugated pi-electrons, electromagnetic spectrum,
highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital
(LUMO), Absorbance , Molar absorptivity, chromophores,
REFERENCES
1. G. M. Barrow, Introduction to Molecular Spectroscopy. McGraw Hill, New York,
1964.
2. P. M. Silverstein, F. X. Wester, Spectroscopy Identification organic compounds, 6th
ed., wiley 1998.
3. W. Kemp, Organic spectroscopy, 3rd ed., MacMillon, 1994.
4. J. R. Dyer, Applications of Absorption Spectroscopy of organic compounds, Prentice
Hall, 1965.
5. Y. R. Sharma, Elementary organic spectroscopy – Principles and Chemical
applications, S. Chand, 1992.

ANSWER TO CHECK POINT 01-01
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=MW4PwJxxyt0
https://www.youtube.com/watch?v=O39avevqndU
WIKIPEDIA
https://en.wikipedia.org/wiki/Ultraviolet%E2%80%93visible_spectroscopy
https://microbenotes.com/uv-spectroscopy-principle-instrumentation-applications/
OER

CREDIT 01-UNIT 02: IR SPECTROSCOPY
LEARNING OBJECTIVES
 Understand the influences of force constants and reduced masses on the frequency
of band vibrations.
 Determine the frequency, wavelength, wavenumber and energy change associated
with an infrared transition.
 Predict the number of fundamental modes of vibration of a molecule.
 State how to make samples for recording the spectra of different organic compounds
 Understand the working of IR-spectrophotometer
 Exposure of recording the IR-spectrum
INTRODUCTION
Vibrational energy of a molecule corresponds to infrared frequency. The interaction of

infrared radiation with molecular vibration gives infrared spectrum. If the average position
and orientation of a molecule remains constant but the distance between the atoms in a
molecule change, molecular vibrations are said to take place.
A vibrational spectrum is observed experimentally as Infrared as well as Raman Spectra.
But the physical origin of two type of spectra are different. Infrared spectrum is associated
with dipole moment ()of the bond whereas Raman spectra are associated with
polarizability.
Either the wavelength ()or wave number in (cm -1) is used to measure the position of a
given infrared absorption. The range of IR spectrum is as :

Most studied absorption frequency in IR spectroscopy is 200 cm–1 4000 cm–1. It is
fundamental frequency region. Greater than 4000 cm–1 requires very high energy. These
are known as overtone bands. Overtones are multiple of fundamental frequencies(e.g.
Apart from fundamental & overtone, we also have combination

bands ( 1 2)
1 2 Addition band (1-2) Substraction band.
01-02-01: BASIC PRINCIPLES

1 Introduction:
The most frequent spectroscopic technique used by organic and inorganic chemists is
Infrared (IR) spectroscopy. It deals with the absorption of radiation in the infrared region of
the electromagnetic spectrum. IR spectrum gives sufficient information about the structure
(identification of functional groups) of a compound and can also be used as analytical tool
to assess the purity of a compound. The absorption of infrared radiation by a molecule
causes changes in their vibrational and rotational energy levels and hence IR -spectroscopy
is also known as vibrational-rotational spectroscopy. Unlike UV-spectroscopy which has
very few peaks in their spectrum, IR spectroscopy provides spectrum with a large number
of absorption bands and hence provide plenty of information about the structure of a
compound. Different bonds present in the spectra correspond to various functional groups
and bonds present in the molecule.
The infrared spectrum can be divided into three main regions: the far infrared (<400cm-1),
the mid-infrared (4000–400 cm−1) and the near-infrared (13000–4000 cm−1). The mid IR
region is of greatest practical use to the organic chemist, but the near - and far-infrared
regions also provide important information about certain materials.
Mid IR region: The mid-infrared spectrum extends from 4000 to 400 cm−1 and results from
vibrational and rotational transitions. This region is most useful for the organic chemist
since most of the organic molecules absorb in this region. The mid -infrared can be divided
into two regions viz functional group region (4000 -1300) and finger print region (1300-
600).
Functional group region (4000-1300): Most of the functional groups present in organic
molecules exhibits absorption bands in the region 4000 -1300 cm-1, hence this is known as
functional group region. In this region each band can be assigned to a particular
deformation of the molecule, the movement of a group of atoms, or the bending or
stretching of a particular bond.
Finger print region (1300-600): The region from 1300 cm-1 to 600 cm-1 usually contains a
very complicated series of absorptions. These are mainly due to molecular vibrations,
usually bending motions that are characteristic of the entire molecule or large fragments of
the molecule. Except enantiomers, any two different compounds cannot have precisely the

same absorption pattern in this region. Thus absorption patterns in this region are unique
for any particular compound that is why this is known as finger print region. It is very
difficult to assign individual bands in this region. Two molecules having the same
functional group may show similar spectra in the functional group region but their spectra
differ in the finger print region. Therefore both the regions are very useful for confirming
the identity of a chemical substance. This is generally accomplished by comparing the
spectrum of an authentic sample. When two compounds show a good match between the IR
spectra in all frequency ranges, mainly in the fingerprint region, strongly indicates tha t they
have the same molecular structures. Both the compounds are alcohols and contain exactly
the same bonds. Now if you compare the infra-red spectra of these compounds, the
functional group region is very similar for both the compounds but the fingerpri nt region is
totally different. Therefore fingerprint region could be crucial to identify the compound. To
understand the importance of finger print region to identify a compound, we can take the
example of propan-1-ol and propan-2-ol.
Both the compounds are alcohols and contain exactly the same bonds. Now if you compare
the infra-red spectra of these compounds, the functional group region is very similar for
both the compounds but the fingerprint region is totally different. Therefore fingerprint
region could be crucial to identify the compound.
Infra-red spectrum of propan-2-ol CH 3 -CH(OH)-CH 3
Near-infrared region (13000–4000 cm−1): The absorptions observed in the near-infrared

region (13000–4000 cm−1) are overtones or combinations of the fundamental stretching
bands. Bands in the near infrared are usually weak in intensity. They are often overlapped
and hence are less useful than the bands in mid -infrared region
NIR shows some similarities to UV-visible spectrophotometry and some to mid -IR
spectrometry. Indeed the spectrometers used in this region are often combined UV-visible-
NIR ones.
Usually Hydrogen-stretching vibrations that occur in the region 3 to 6 µm, are the
absorption bands due to overtones (or combination) of fundamental bands

NIR is generally used for quantitative organic functional -group analysis. The NIR region
has also been used for qualitative analyses and studies of hydrogen bonding, solute -solvent
interactions, organometallic compounds, and inorganic compounds
Far-infrared region (600-100 cm-1 ): The far-infrared spectrum extends from 600 to 100
cm−1 . Organometallic and inorganic molecules contain heavy atoms and have weak bonds ,
therefore the fundamental vibrations of these molecules fall in this reigon. Lattice
vibrations of crystalline materials occur in this region.
2. Origin of Infra-red Spectroscopy:
IR-spectroscopy gives the information about molecular vibrations or more precisely on
transitions between vibrational and rotational energy levels. Since the absorption of
infrared radiation leads to transition between vibrational and rotational energy levels, it is
also vibrational-rotational spectroscopy.
When a molecule absorb IR-radiation below 100 cm-1 , transitions between rotational
energy levels takes place. Since these energy levels are quantized, a rotational spectrum
consists of discrete lines. If a molecule absorbs radi ation in the range 100-10,000 cm-1 , it
causes transitions between vibrational energy levels. These energy levels are also quantised
but vibrational spectra appear as bands rather than discrete lines. Each vibrational energy
level is associated with a large number of closely spaced rotational energy levels or we can
say that the energy difference between various rotational energy levels is very short than
the energy difference between various vibrational energy levels. Therefore the vibrational
spectra appear s vibrational-rotational bands instead of discrete lines. Organic chemists are
mainly concerned with these transitions especially with those occur in the range 4000 -667
cm-1 .
3. Molecular Vibrations:
The atoms in a molecule do not remain fixed at certa in positions. The two nuclei can
vibrate backwards and forwards or towards and away from each other around an average
position. There are two types of fundamental molecular vibrations viz stretching (change in
bond length) and bending (change in bond angle ).
Stretching vibrations: It involves a rhythmic movement along a bond axis with a subsequent
increase and decrease in bond length. Stretching vibrations are of two types viz
Symmetrical Stretching and asymmetrical stretching.

Bending vibrations: It involves a change in bond angle or movement of a group of atoms
with respect to the rest of the molecule. Bending vibrations are of four types.
i) Rocking ii) Scissoring iii) Wagging iv) Twisting
All the bonds in a molecule are not capable of absor bing infrared radiation but only those
bonds which are accompanied by a change in the dipole moment will absorb in the infra -red
region. Thus, vibrations which are associated with the change in the dipole moment of the
molecule are called infra-red active transitions otherwise the vibration is said to be IR -
inactive and do not show any absorption band in the IR -spectrum. Generally, larger the
change in the dipole moment, the higher is the intensity of absorption. Hence the
vibrational absorption bands in simple hydrocarbons are weak while bands associated with
bonds connecting atoms with considerable electronegativity difference give strong bands.
4. Selection Rule:
IR-radiation is absorbed only when a change in dipole moment of the molecule
takes place. Complete symmetry about a bond may eliminate certain absorption
bands. Therefore number of absorption bands observed is not exactly equal to
the fundamental vibrations, some of the fundamental vibrations are IR -active
while others are not. This is governed by se lection rule described below
1) In a molecule with a centre of symmetry, the vibrations symmetrical about the
centre of symmetry are IR-inactive
2) The vibrations which are not symmetrical about the centre of symmetry are IR -
active.
Here are some examples which could explain the selection rule.
a) All the symmetrical diatomic molecules such as H2, N2 and Cl2 etc. are IR -
inactive.
b) The symmetrical stretching of the C=C bond in ethylene (centre of
symmetry) is IR-inactive.
c) The symmetrical stretching in CO2 is IR-inactive, whereas asymmetric
stretching is IR-active.
d) Cis-dichloro-ethylene molecule shows C=C stretching bands whereas trans
molecule does not show this band.
5. Fundamental Vibrations:

The IR spectrum of a compound may show more than one vibrational absorp tion bands.
The number of these bands corresponds to the number of fundamental vibrations in the
molecule which can be calculated from the degree of freedom (DOF) of the molecule. A
molecule comprising of n atoms has a total of 3n DOF. In a nonlinear molec ule, three of
these degrees of freedom are rotational and three are translational and the remaining (3n -6)
correspond to vibrational degree of freedom or fundamental vibrations. Whereas in a linear
molecule, only two degrees of freedom are rotational (beca use rotation about its axis of
linearity does not change the positions of the atoms) and three are translational. The
remaining (3n-5) degrees of freedom are vibrational degree of freedom or fundamental
vibrations.
Simple diatomic molecules have only 1 bond and only 1 vibrational band. If the molecule is
symmetrical such as hydrogen, nitrogen, and chlorine, the band is not observed in the IR
spectrum. Asymmetrical diatomic molecules, e.g. CO and iodine chloride absorb in the IR
spectrum.
It has been observed that in actual IR spectrum, the theoretical number of fundamental
bands is seldom observed because there are certain factors which may increase or decrease
the number of bands. Some fundamental vibrations lie outside the IR region (4000 -400 cm-
1 ), whereas some are too weak to be observed. Few fundamental vibrations are too close
that they merge into one another. The occurrence of degenerate bands (bands of same
frequency) also cause decrease in the fundamental vibrational bands.
For example: Carbon dioxide, CO2 is linear and has four fundamental vibrations but
actually it shows only two bands (666 cm–1 and 2350 cm–1 ). The symmetrical stretching
vibration of CO2 is inactive in the IR because this vibration produces no change in the
dipole moment of the molecule. The two scissoring or bending vibrations are equivalent and
therefore have the same frequency (degenerate) at 666 cm–1 . The asymmetrical stretch of
CO2 gives a strong band in the IR at 2350 cm–1.
Fig : Stretching & Bending Vibrational modes for CO 2

The appearance of certain types of non-fundamental (overtones, combinations of
fundamental vibrations or difference of fundamental vibrations) bands increases the number

of bands as compared to that expected from the theoretical number of fundamental bands.
All these bands have very weak intensity than the fundamental vibration bands.
Overtones bands: In addition to the fundamental vibrations, other frequencies can be
generated by modulations of the fundamental bands. An overtone band occurs when the
molecule makes a transition from the ground state (v=0) to the second excited state (v=2),
where v is the vibrational quantum number. The intensity of the overtone band is very low
as compared to the fundamental band and they are usually found in the near infrared region.
Based on the harmonic oscillator approximation it has been found that the energy of the
overtone transition is about n times of the fundamental vibration associated with that
particular transition. Suppose a compound shows strong absorptions at x and y cm-1 then it
may also give rise to weaker absorptions at 2x, 2y, 3x and 3y cm -1, respectively. The
intensity of overtones bands decreases as the order of the overtone increases, i.e. the
intensity of 3x or 3y overtones will be less than the 2x and 2y. Therefore second and third
overtones are rarely observed.
Combination Bands: Combination bands are observed when two or more than two
fundamental vibrations are excited simultaneously. If there are two fundamental vibrations
at x and y cm-1 then it may also give rise to absorption bands at (x+y), (x+2y), (2x+y) cm -1
.
Difference bands: It is also possible to have a difference band where the frequencies of two
fundamental bands are subtracted, i.e. (x-y), (x-2y), (2x-y) cm-1 .
Fermi bands/resonance: When a fundamental vibration couples with an overtone or
combination band, the coupled vibration is called Fermi resonance. As a result, two strong
bands are observed in the spectrum, instead of the expected strong and we ak bands. Fermi
resonance is often observed in carbonyl compounds.
A practical use for understanding overtones and combination bands is applied to organic
solvents used in spectroscopy. Most organic liquids have strong overtone and combination
bands in the mid-infrared region, therefore, acetone, DMSO, or acetonitrile should only be
used in very narrow spectral regions. Solvents such at CCl4, CS2 and CDCl3 can be used
above 1200 cm-1.
6. Sample Preparation:
IR spectrum of a compound can be recorded in many di fferent forms, such as liquid,
solid, gas and solution. Some of the materials are opaque to infrared radiation, so in
order to obtain spectra they must be dissolved or diluted in a transparent matrix. For
recording IR spectra, the sample should be properly dry as water absorb near 3710 and
1630 cm-1 . The samples should be perfectly dried, since cell materials (NaCl, KBr) are
usually spoiled by the moisture.
1) Solid samples: There are several methods by which an IR spectrum of a solid sample
can be recorded.

a) As a pressed disc: The first common method involves the mixing of finely
ground solid sample with powdered potassium chloride. A translucent pellet of
this powder mixture is formed by pressing it in a mechanical pressure. The main
advantage of using KBr is that it does not interfere with the bands due to
compound since KBr is transparent to IR radiation 4000 -650 cm-1 and thus gives
better spectra. The disadvantage of this method is that KBr absorbs water quickly
which may interfere with the spectra that is obtained.
b) As a mull or paste: Finely ground compound is mixed with an oily mulling agent
(usually Nujol) using a pestle and mortar. A thin film of the mull is placed
between two flat plates of NaCl and the spectrum is measured. The main
disadvantages of this method is that nujol has absorption bands at 2924 -2860,
1462, 1380 cm-1, therefore no information about the observed compound can be
obtained in this region.
c) As a film: The third method is to dissolve the soild sample in a suitable, non -
hygroscopic solvent usually methylene chloride or carbon tetra chloride. A drop
of this solution is deposited on surface of Potassium bromide or Sodium chloride
plate. The solution is then evaporated to dryness and the film thus formed on the
KBr disc is analysed directly to obtain the IR spectrum. The most important
thing is that the film should not be too thick otherwise light cannot pass through
it. This method gives good results with dilute solution of the compound in a non -
polar solvent.
2) Liquid samples: Liquids are studied neat or in solution. A drop of neat liquid sample
or a solution of the sample in an appropriate solvent is placed between two plates of
a salt (sodium chloride or potassium bromide) to give a thin film and analysed to
obtain the spectrum. The plates are transparent to the infrared light and do not
introduce any lines onto the spectra. Salt plates break easily and are water soluble
therefore compounds analysed by this method should be free from water. Spectrum
obtained by this method is known as neat spectrum since no solvent is used in
recording the spectrum.
3) Gaseous samples: The gas is introduced into a special cell with a long path length
and the walls of its both the ends are normally made up of NaCl. Gases have very
less densities compared to liquids, and hence path lengths should be correspondingly
greater, usually 10 cm or longer. The vapor phase technique is limited because most
of the organic compounds have too low vapor pressure to produce a useful
absorption spectrum.
It is important to note that spectra obtained from different sample preparation
methods will look slightly different from each other due to differences in the
samples' physical states.

SOLVED PROBLEMS 01
9) Which of the following statements about infrared spectroscopy is correct?
a.) When the frequency of infrared light matches the frequency of bond vibration in a molecule,
a peak appears on the spectrum.
b.) Infrared spectroscopy can be used to determine the size and shape of a compound’s carbon
skeleton.
c.) An IR spectrometer illuminates a compound with infrared light and records the positions
where the light is blocked by the compound. This results in the peaks of the spectrum.
d.) The fingerprint region of the spectrum can be used to identify functional groups.
Correct Answer – a.) When the frequency of infrared light matches the frequency
of bond vibration in a molecule, a peak appears on the spectrum
10) In an infrared (IR) spectrum, which of the following functional groups has the highest
frequency?
a.) Ketone
b.) Aldehyde
c.) Ester
d.) Alcohol
Correct Answer – d) Alcohol.
17) What is the range of the infrared spectrum?
Answer – The infrared spectrum extends from 700 to 1000 nm (wavelength), or 14,286 to 12,800
cm–1 (wavenumber).
18) What is the fundamental measurement in IR spectroscopy?
Answer – An infrared spectrum is a plot between measured infrared intensity versus wavelength
(or frequency) of light, which is the fundamental measurement obtained in infrared spectroscopy.
01-02-02: IR-SPECTROMETER
Traditionally, dispersive infrared spectrophotometers, developed in 1940s, were used to
obtain infrared spectra. In 1960s, a new method was developed known as Fourier -transform
infrared (FT-IR) spectrometers. But due to high cost of the instrument, this was tended to
be used for advanced research only at that time. Gradually, technology advancements in
computers and instruments have reduced the cost and enhanced the capabilities of an FT-IR
spectrophotometer. Today they are predominantly used and have improved the acquisition
of infrared spectra dramatically.
1. Dispersive Infrared Spectrometer:
The basic components of a dispersive IR spectrometer include a radiation source,
Sample and reference cells, monochromator, detector, amplifier and recorder. A schematic
diagram of a typical dispersive spectrometer is shown in Fig.
Radiation source: The common IR radiation source are inert solids that are heated
electrically to 1000 to 1800 °C to promote thermal emission of radiation i n the infrared
region of the EM spectrum. The most common sources are Nernst filament (composed of
rare-earth oxides such as zirconium, cerium and thorium), Globar (composed of silicon
carbide), and Nichrome coil. They all produce continuous radiations, bu t with different

radiation energy profiles. The beam from the source is divided into two equivalent beams,
one passing through the sample and the other as reference beam.
Sample and reference cells: Like UV sample tubes (cuvettes) glass or quartz cannot be used
to make the sample cells for IR-spectroscopy, because they absorb strongly in most of the
IR region. Alkali metal halides such as KCl, NaCl are commonly used as they are
transparent to the IRregion.
Monochromator: The monochromator is a device used t o disperse or separate a broad
spectrum of IR radiation into a continuous spectrum of frequencies of Infrared light. The
monochromator consists of rapidly rotating chopper that passes the two beams alternately to
a diffraction grating. The slowly rotating diffraction grating varies the frequency or
wavelength of radiation and sends it the individual frequency to the thermocouple detector
which generates an electrical signal as a response.
Detectors and Amplifier: Detectors are devices that convert the radia nt energy into an
electrical signal. The detector determines the ratio between the intensities of the reference
and sample beams. Due to the difference in the intensities of the two beams falling on the
detector, an alternating current starts flowing from the detector to the amplifier, where it is
amplified and relayed to the recorder.
The detectors used in IR spectrometers can be categorized into two classes: thermal
detectors and photon detectors. Thermal detectors consists of several thermocouples
connected together to produce greater sensitivity. They measure the heating effect produced
by infrared radiation that causes the flow of current. The current produced is proportional
to the intensity of radiation falling on the thermal detector. Photon detector s rely on the
interaction of IR radiation and a semiconductor material. Non -conducting electrons are
excited to a conducting state and therefore producing a small current or voltage.
Recorder: It records IR-spectrum as a plot of frequency of absorbed radia tion and intensity
of absorption in terms of transmittance. Unlike UV-spectroscopy, here we use the
wavenumber unit. As the detector records the ratio of the intensities of the two beams
therefore percent transmittance is recorded.
Transmittance (T) = I/I0
Percent transmittance (%T) = I/I0 X 100
Where I0 is the intensity of the incident radiation and I is the intensity of the radiation
emerging from the sample.

Fig : Schematic diagram of a dispersive IR spectrometer
2. Fourier-Transform Infrared Spectrometer:
Fourier transform spectrometers have recently replaced dispersive instruments for most
applications due to their superior speed and sensitivity. They have greatly extended the
capabilities of infrared spectroscopy and have been applied to many areas that are very
difficult or nearly impossible to analyze by dispersive instruments. Instead of viewing each
component frequency sequentially, as in a dispersive IR spectrometer, all frequencies are
examined simultaneously in Fourier transform infrared (FTIR) spectroscopy.
The basic components of an FTIR spectrometer are shown schematically in Figure 2.3. The
radiation emerging from the source is passed through an interferometer to the sample before
reaching a detector. Then the signal is amplif ied and converted to digital form by an analog-
todigital converter and transferred to the computer in which Fourier transform is carried
out. Interferometer divides radiant beams, generates an optical path difference between the
beams and then recombines them in order to produce repetitive interference signals
measured as a function of optical path difference by a detector. Thus interferometer
produces interference signals, which contain infrared spectral information generated after
passing through a sample.
The most commonly used interferometer is a Michelson interferometer. It consists of three
active components: a moving mirror, a fixed mirror, and a beam splitter (Fig. 15.4). The
two mirrors are perpendicular to each other. The beam splitter is a semi -reflecting device
and bisects the plane of these two mirrors. The beam splitter is often made by coating a thin
film of germanium or iron oxide onto an ‘infrared -transparent’ substrate such as potassium
bromide or cesium iodide.
The energy goes from the source to the beam splitter which splits the beam into two parts.
One part is transmitted to a moving mirror; one part is reflected to a fixed mirror. The
moving mirror moves back and forth at a constant velocity. The two beams are reflected
from the mirrors and recombined at the beam splitter. The beam from the moving mirror has
traveled a different distance than the beam from the fixed mirror. When the beams are
combined an interference pattern is created. Since some of the wavelengths recombine
constructively and some destructively. This interference pattern is called an interferogram.

This interferogram then goes from the beam splitter to the sample, where some energy is
absorbed and some is transmitted. The transmitted portion reaches the detector. The
detector reads information about every wavelength in the infrared range simultaneously.
The moving mirror produces an optical path difference between the two arms of the
interferometer (the relative position of moving mirror to the fixed mirror). If the two
mirrors are at equal distance from the beam splitter, the two beams travel the same path
length. Therefore two beams are totally in phase with each other and hence they interfere
constructively and lead to a maximum intensity reaching to the detector. When the moving
mirror travels in either direction by the distance λ/4, the optical path is changed by 2 (λ/4),
or λ/2. The two beams are 180° out of phase with each other, and thus interferes
destructively resulting minimum intensity reaching the detector. If the moving mirror
further travels by λ/4, then the optical path difference will be 2 (λ/2), or λ. The two beams
are again in phase with each other and result in another constructive interference again
giving a maximum response in the detector. Such a maximum will be observed w henever
the path difference is an integral multiple of λ.
Thus moving mirror is the key component of interferometer, because alternate light and
dark images will reach the detector if the mirror is slowly moved either away from or
towards the beam splitter. When the mirror is moved at a constant velocity, the intensity of
radiation reaching the detector varies in a sinusoidal manner to produce the interferogram
output shown in Fig. 15.4. The interferogram is a complex signal but its wave like pattern
contains all the frequencies that make up the infrared spectrum. It is actually a time domain
spectrum and records the detector response changes versus time. If the sample happens to
absorb at this frequency, the amplitude of the sinusoidal wave is reduced by an amount
proportional to the amount of sample in the beam.

Now to obtain the infrared spectrum, the detector signal is sent to the computer, where
mathematical operation known as Fourier transformation converts the interferogram (a time
domain spectrum displaying intensity versus time) to the final IR spectrum, a frequency
domain spectrum showing plot between intensity of signal versus frequency.
3. Hands-on Operation of an FTIR Spectrometer:
Step 1: First step is the sample preparation. Sample preparatio n has already been
discussed in the above section.
Step 2: The second step is to obtain an inter fero gram of the background which consists of
the IR active atmospheric gases carbon dioxide (doublet at 2360 cm –1 and sharp spike at
667 cm–1 in Fig. 6) and water vapors (two irregular groups of lines at about 3600 cm –1 and
about 1600 cm–1 in Fig. 6). Nitrogen and oxygen are not IR -active hence do not absorb in
IR-region. This inter fero gram is subjected to Fourier transform which gives the spectrum
of background. Figure 6 shows an example of an FTIR background spectrum.
Step 3: In the third step, spectrum of the sample under investigation is obtained by the same
procedure. This spectrum contains absorption bands from the sample as well as the
background (gaseous or solvent).
Step 4: The ratio between the single-beam sample spectrum and the single beam
background spectrum gives the spectrum of the sample (Figure 7). Computer software
automatically subtracts the spectrum of the background from the sample spectr um.
Step 5: Finally the data obtained is analyzed by assigning the observed absorption
frequency bands in the sample spectrum to appropriate normal modes of vibrations in the
molecules.
SOLVED PROBLEMS 02
18) A carbonyl group will cause a sharp dip at about ____ cm–1.
a) 1700
b) 2800
c) 3400
d) 1200

19) Which of the following causes the vibration of atoms?
a) The number of protons contained in a nucleus.
b) Electron movement to higher energy levels.
c) The molecule’s total molecular weight.
d) Dipole moments between atoms.
20) Which solvent is ideal for infrared spectroscopy?
Answer – Carbon Tetrachloride (CCl 4) and Carbon Disulfide (CS 2) are the most commonly
used solvents. Polar materials can be dissolved in chloroform, methylene chloride,
acetonitrile, and acetone.
21) What are the different types of infrared spectroscopy?
The two types of infrared spectrometers are:
 The dispersive infrared spectrometer (DS)
 The Fourier transform infrared spectrometer (FTIS).
22) Explain why a thermal detector is not suitable for use in an FTIR instrument.
23) In your own words, describe how a pyroelectric detector works.
01-02-03: ELECTROMAGNETIC RADIATION

Infrared spectroscopy is certainly one of the most important analytical techniques available
to today’s scientists. One of the great advantages of infrared spectroscopy is that virtually
any sample in virtually any state may be studied. Liquids, solutions, pastes, powders, f ilms,
fibres, gases and surfaces can all be examined with a judicious choice of sampling
technique. As a consequence of the improved instrumentation, a variety of new sensitive
techniques have now been developed in order to examine formerly intractable sam ples.
1.1 Electromagnetic Radiation:
The visible part of the electromagnetic spectrum is, by definition, radiation visible to the
human eye. Other detection systems reveal radiation beyond the visible regions of the
spectrum and these are classified as radiowave, microwave, Introduction 3 infrared,
ultraviolet, X-ray and γ-ray. These regions are illustrated in Figure 1.1, together with the
processes involved in the interaction of the radiation of these regions with matter. The
electromagnetic spectrum and the varied interactions between these radiations and many
forms of matter can be considered in terms of either classical or quantum theories.
The nature of the various radiations shown in Figure 1.1 have been interpreted by
Maxwell’s classical theory of electro- and magneto-dynamics – hence, the term
electromagnetic radiation. According to this theory, radiation is considered as two mutually
perpendicular electric and magnetic fields, oscillating in single planes at right angles to
each other. These fields are in phase and are being propagated as a sine wave, as shown in

Figure 1.2. The magnitudes of the electric and magnetic vectors are represented by E and B,
respectively.
A significant discovery made about electromagnetic radiation was that the velocity of
propagation in a vacuum was constant for all regions of the spectrum. This is known as the
velocity of light, c, and has the value 2.997 925 × 108 m s−1. If one complete wave
travelling a fixed distance each cycle is visualized, it may be o bserved that the
velocity of this wave is the product of the wavelength, λ (the distance between adjacent
peaks), and the frequency, ν (the number of cycles
Figure 1.1 Regions of the electromagnetic spectrum.
Figure 1.2 Representation of an electromagnetic wave

per second). Therefore: c = λν (1.1)
The presentation of spectral regions may be in terms of wavelength as metres or sub -
multiples of a metre. The following units are commonly encountered in spectroscopy:
1 A˚ = 10−10 m 1 nm = 10−9 m 1 µm = 10−6 m
Another unit which is widely used in infrared spectroscopy is the wavenumber, ν, in cm−1.
This is the number of waves in a length of one centimetre and is given b y the following
relationship: ν = 1/λ = ν/c (1.2)
This unit has the advantage of being linear with energy. During the 19th Century, a
number of experimental observations were made which were not consistent with the
classical view that matter could interact with energy in a continuous form. Work by
Einstein, Planck and Bohr indicated that in many ways electromagnetic radiation could be
regarded as a stream of particles (or quanta) for which the energy, E, is given by the Bohr
equation, as follows: E = hν (1.3)
where h is the Planck constant (h = 6.626 × 10−34 J s) and ν is equivalent to the classical
frequency.

Processes of change, including those of vibration and rota tion associated with infrared
spectroscopy, can be represented in terms of quantized discrete energy levels E0, E1, E2,
etc., as shown in Figure 1.3. Each atom or molecule in a system must exist
in one or other of these levels. In a large assembly of molec ules, there will be a distribution
of all atoms or molecules among these various energy levels. The latter are a function of an
integer (the quantum number) and a parameter associated with the particular atomic or
molecular process associated with that state. Whenever a molecule interacts with radiation,
a quantum of energy (or
Figure 1.3 Illustration of quantized discrete energy levels.

photon) is either emitted or absorbed. In each case, the energy of the quantum of radiation
must exactly fit the energy gap E1 − E0 or E2 − E1, etc. The energy of the quantum is
related to the frequency by the following:
E = hν (1.4)
Hence, the frequency of emission or absorption of radiation for a transitio n between the
energy states E0 and E1 is given by:
ν = (E1 − E0)/h (1.5)
Associated with the uptake of energy of quantized absorption is some deactivation
mechanism whereby the atom or molecule returns to its original state. Associated with the
loss of energy by emission of a quantum of energy or photon is some prior excitation
mechanism. Both of these associated mechanisms are represented by the dotted lines in
Figure 1.3.
1.2 Infrared Absorptions :

For a molecule to show infrared absorptions it must possess a specific feature, i.e. an
electric dipole moment of the molecule must change during the vibration. This is the

selection rule for infrared spectroscopy. Figure 1.4 illustrates an example of an ‘infrare d-
active’ molecule, a heteronuclear diatomic molecule. The dipole moment of such a molecule
changes as the bond expands and contracts. By comparison, an example of an ‘infrared -
inactive’ molecule is a homonuclear diatomic molecule because its dipole moment remains
zero no matter how long the bond. An understanding of molecular symmetry and group
theory is important when initially assigning infrared bands. A detailed description of such
theory is beyond the scope of this book, but symmetry and group theory a re discussed in
detail in other texts [1, 2]. Fortunately, it is not necessary to work from first principles each
time a new infrared spectrum is obtained.
Infrared absorptions are not infinitely narrow and there are several factors that contribute to
the broadening. For gases, the Doppler effect, in which radiation is shifted in frequency
when the radiation source is moving towards or away from the observer, is a factor. There is
also the broadening of bands due to the collisions between molecules. Anoth er source of
line broadening is the finite lifetime of the states involved in the transition. From quantum
mechanics, when the Schrodinger equation is solved for a system which is changing with
time, the ¨ energy states of the system do not have precisely defined energies and this leads
to lifetime broadening. There is a relationship between the lifetime of an excited state and
the bandwidth of the absorption band associated with the transition to the excited state, and
this is a consequence of the Heisenberg Uncertainty Principle. This relationship
demonstrates that the shorter the lifetime of a state, then the less well defined is its energy.
SOLVED PROBLEMS 03
24) Convert each of the following frequencies into wavenumbers
a. 4.98 X 1013 Hz b. 6.24 X 1013 Hz c. 1.2 X 1013 Hz d. 1.2 X 1014 Hz e. 9.0 X 1013
Hz f. 2.4 X 1013 Hz
a) Solution(a) c = λν 2.998 x 108 m/s = (λ)(4.98 x 1013 s -1 ) λ = 6.020 x 10-6 m =
6.020 x 10-4 cm 𝜈̅ = 1/6.020 x 10-4 cm = 1661 cm-1 = 1660 cm-1
(d) c = λν 2.998 x 108 m/s = (λ)(1.2 x 1013 s -1 ) λ = 2.498 x 10-5 m = 2.498 x 10-3
cm 𝜈̅ = 1/2.498 x 10-3 cm = 400.266 cm-1 = 4.0 x 102 cm-1
25) Convert each of the following wavenumbers into (i) wavelength (in μm); (ii) frequency
(in Hertz, s -1 ), and (iii) energy (J).
a. 3000 cm-1 b. 4000 cm-1 c. 1710 cm-1 d. 2100 cm-1 e. 800 cm-1 f. 1500 cm-1

a) Solution (d) 2100 cm-1 (i) μm = (2100 cm-1 ) -1 x (1 m/100 cm) x (106 μm / m) =
4.76 μm ≈ 4.8 μm (ii) c=λν (2.998x108 m/s) = (4.76 x 10 -6 m)ν ν = 6.295 x 1013 =
6.3 x 1013 Hz (iii) E = hν = (6.626 x 10-34 Js)(6.295 x 1013 s -1 ) = 4.172 x 10-20
= 4.2 x 10-20 J
b) (d) 800 cm-1 (i) μm = (800 cm-1 ) -1 x (1 m/100 cm) x (106 μm / m) = 12.5 μm ≈ 13
μm (ii) c=λν (2.998x108 m/s) = (12.5 x 10-6 m)ν ν = 2.398 x 1013 = 2.4 x 1013 Hz
(iii) E = hν = (6.626 x 10-34 Js)(2.398 x 1013 s -1 ) = 1.589 x 10-20 = 1.6 x 10-20 J
26) What is the region of the infrared spectrum?
The majority of the bands that indicate which functional group is present are found between 4000
cm–1 and 1300 cm–1. Their bands can be identified and used to determine the functional group of
an unknown compound functional group. The fingerprint region, from 1300 cm –1 to 400 cm–1,
contains bands that are unique to each molecule, similar to a fingerprint. These bands are only
used to compare the spectra of different compounds.
27) How does infrared spectroscopy work?
– Infrared (IR) spectroscopy excites the molecules of a compound and produces an infrared
spectrum of the energy absorbed by a molecule as a function of the frequency or wavelength of
light. Different types of bonds react differently to IR radiation. Triple and double bonds, for
example, are shorter and stiffer than single bonds and thus vibrate at higher frequencies. The
types of atoms in the bonds are also important. Because O-H bonds are stronger than C-H bonds,
they vibrate at higher frequencies. As a result, IR spectroscopy allows us to identify the various
functional groups present in a compound.
28) Why are deviations from Beer’s law more common in IR spectroscopy than in UV-vis
spectroscopy?
29) In your own words, discuss the considerations one must make when selecting a suitable
source for FTIR spectroscopy?
01-02-04: NORMAL MODES OF VIBRATION

1.3 Normal Modes of Vibration:
The interactions of infrared radiation with matter may be understood in terms of changes in
molecular dipoles associated with vibrations and rotations. In order to begin with a basic
model, a molecule can be looked upon as a system of masses joined by bonds with spring -
like properties. Taking first the simple case of diatomic molecules, such molecules have
three degrees of translational freedom and two degrees of rotational freedom. The atoms in
the molecules can also move relative to one other, that is, bond lengths can vary or one
atom can move out of its present plane. This is a description of stretching and bending
movements that are collectively referred to as vibrations. For a diatomic molecule, only one
vibration that corresponds to the stretching and compression of the bond is possible. This

accounts for one degree of vibrational freedom. Polyatomic molecules contai ning many (N)
atoms will have 3N degrees of freedom. Looking first at the case of molecules containing
three atoms, two groups of triatomic molecules may be distinguished, i.e. linear and non -
linear. Two simple examples of linear and non-linear triatomics are represented by CO2
Fig : H 2 O & CO 2 Molecules

and H2O, respectively (illustrated in Figure). Both CO 2 and H 2 O have three degrees of
translational freedom. Water has three degrees of rotational freedom, but the linear
molecule carbon dioxide has only two since no detectable energy is involved in rotation
around the O=C=O axis. Subtracting these from 3N, there are 3N−5 degrees of freedom for
CO2 (or any linear molecule) and 3N−6 for water (or any non -linear molecule). N in both
examples is three, and so CO2 has four vibrational modes and water has three. The degrees
of freedom for polyatomic molecules are summarized in Table.
Whereas a diatomic molecule has only one mode of vibration which corresponds to a
stretching motion, a non-linear B–A–B type triatomic molecule has three modes, two of
which correspond to stretching motions, with the remainder corresponding to a bending
motion. A linear type triatomic has four modes, two of which have the same frequency, and
are said to be degenerate. Two other concepts are also used to explain the frequency of
vibrational modes. These are the stiffness of the bond and the masses of the atoms at each
end of the bond. The stiffness of the bond can be characterized by a proportionality
constant termed the force constant, k (derived from Hooke’s law). The reduced mass, µ,
provides a useful way of simplifying our calculations by combining the individual atomic
masses, and may be expressed as follows:
(1/µ) = (1/m1) + (1/m2) (1.6)
where m1 and m2 are the masses of the atoms at the ends of the bond. A practical
alternative way of expressing the reduced mass is:
µ = m1m2/(m1 + m2) (1.7)
The equation relating the force constant, the reduced mass and the frequency of absorption
is: ν = (1/2π) √(k/µ)(1.8)

This equation may be modified so that direct use of the wavenumber values for bond
vibrational frequencies can be made, namely: ν = (1/2πc)√(k /µ) (1.9)
where c is the speed of light.
A molecule can only absorb radiation when the incoming infrared radiation is of the same
frequency as one of the fundamental modes of vibration of the molecule. This means that
the vibrational motion of a small part of the molecule is increased while the rest of the
molecule is left unaffected.
Vibrations can involve either a change in bond length (stretching) or bond angle
(bending) (Figure 1.6). Some bonds can stretch in-phase (symmetrical stretching) or out-of-
phase (asymmetric stretching), as shown in Figure 1.7. If a molecule has different terminal
atoms such as HCN, ClCN or ONCl, then the two stretching modes are no longer symmetric
and asymmetric vibrations of similar bonds, but will have varyi ng proportions of the
stretching motion of each group. In other words, the amount of coupling will vary.
Bending vibrations also contribute to infrared spectra and these are summarized in Figure
1.8. It is best to consider the molecule being cut by a p lane through the hydrogen atoms and
the carbon atom. The hydrogens can move in the same direction or in opposite directions in
this plane, here the plane of the page. For more complex molecules, the analysis becomes
simpler since hydrogen atoms may be considered in isolation because they are usually
attached to more massive, and therefore, more rigid parts of the molecule. This results in
in-plane and out-of-plane bending vibrations, as illustrated in Figure 1.9. As already
mentioned, for a vibration to give rise to the absorption of infrared radiation, it must cause
a change in the dipole moment of the molecule. The larger this change, then the more

intense will be the absorption band. Because of the difference in electronegativity between
carbon and oxygen, the carbonyl group is permanently polarized, as shown in Figure 1.10.
Stretching this bond will increase the dipole moment and, hence, C=O stretching is an
intense absorption. In CO2, two different stretching vibrations are possible: (a) symmetric
and (b) asymmetric (Figure 1.11). In practice, this ‘black and white’ situation does not
prevail. The change in dipole may be very small and, hence, lead to a very weak absorption.
DQ 1.1
Which one of the vibrations shown in Figure 1.11 is ‘infrared -inactive’?
Answer: A dipole moment is a vector sum. CO2 in the ground state, therefore, has no
dipole moment. If the two C=O bonds are stretched symmetrically, there is still no net
dipole and so there is no infrared activity. However, in the asymmet ric stretch, the two C=O
bonds are of different length and, hence, the molecule has a dipole. Therefore, the vibration
shown in Figure 1.11(b) is ‘infrared-active’.

Symmetrical molecules will have fewer ‘infrared-active’ vibrations than asymmetrical
molecules. This leads to the conclusion that symmetric vibrations will generally be weaker
than asymmetric vibrations, since the former will not lead to a change in dipole moment. It
follows that the bending or stretching of bonds involving atoms in wid ely separated groups
of the periodic table will lead to intense bands. Vibrations of bonds such as C –C or N=N
will give weak bands. This again is because of the small change in dipole moment
associated with their vibrations. There will be many different vi brations for even fairly
simple molecules. The complexity of an infrared spectrum arises from the coupling of
vibrations over a large part of or over the complete molecule. Such vibrations are called
skeletal vibrations. Bands associated with skeletal vibr ations are likely to conform to a
pattern or fingerprint of the molecule as a whole, rather than a specific group within the
molecule.
1.4 Complicating Factors:
There are a number of factors that may complicate the interpretation of infrared spectra.
These factors should be considered when studying spectra as they can result in important
changes to the spectra and may result in the misinterpretation of bands.
1.4.1 Overtone and Combination Bands
The sound we hear is a mixture of harmonics, that is, a funda mental frequency mixed with
multiples of that frequency. Overtone bands in an infrared spectrum are analogous and are
multiples of the fundamental absorption frequency. The energy levels for overtones of
infrared modes are illustrated in Figure 1.13. The e nergy required for the first overtone is
twice the fundamental, assuming evenly spaced energy levels. Since the energy is
proportional to the frequency absorbed and this is proportional to the wavenumber, the first
overtone will appear in the spectrum at twice the wavenumber of the fundamental.
Combination bands arise when two fundamental bands absorbing at ν1 and ν2 absorb energy
simultaneously. The resulting band will appear at (ν1 + ν2) wavenumbers.

1.4.2 Fermi Resonance:
The Fermi resonance effect usually leads to two bands appearing close together when
only one is expected. When an overtone or a combination band has the same frequency as,
or a similar frequency to, a fundamental, two bands appear, split either side of the expected
value and are of about equal intensity. The effect is greatest when the frequencies match,
but it is also present when there is a mismatch of a few tens of wavenumbers. The two
bands are referred to as a Fermi doublet.
1.4.3 Coupling:
Vibrations in the skeletons of molecules become coupled, as mentioned in Section 1.4.
Such vibrations are not restricted to one or two bonds, but may involve a large part of the
carbon backbone and oxygen or nitrogen atoms if present. The energy levels mix, hence
resulting in the same number of vibrational modes, but at different frequencies, and bands
can no longer be assigned to one bond. This is very common and occurs when adjacent
bonds have similar frequencies. Coupling commonly occurs between C –C stretching, C–O
stretching, C–N stretching, C–H rocking and C–H wagging motions. A further requirement
is that to be strongly coupled, the motions must be in the same part of the molecule.
1.4.4 Vibration–Rotation Bands:
When the infrared spectra of gaseous heteronuclear molecules are analysed at high
resolution, a series of closely spaced components are observed. This type of structure is due
to the excitation of rotational motion during a vibrational transition and is referred to as an
vibration– rotation spectrum [1]. The absorptions fall into groups called branches and are
labelled P, Q and R according to the change in the rotational quantum number associated
with the transition. The separation of the lines appearing in a vibration – rotation spectrum
may be exploited to determine the bond length of the molecule being examined.

APPLICATIONS:
IR spectroscopy is applied for qualitative as well as quantitative analysis of drugs in
Pharmaceutical industry.
 It is used for identification of drug substances
 It identifies the impurities present in a drug sample
 It helps in study of hydrogen bonding both intermolecular and intramolecular type.
 It is widely used in study of polymers.
 It helps determining issue of Cis- Trans isomers present in a mixture of compounds.
 It elucidates reaction mechanisms.
 It is a great tool investigation of rotational isomerism.
 It identifies functional groups present in any sample.
 It estimates relative stability of confirmation.
 It distinguishes between Sis and trance I so much.
 It can predict the keto-enol tautomerism.
 It helps in establishing quality of tea leaves.
SOLVED PROBLEMS 04
30) How does you differentiate the following each pair using IR spectra ?
(a) Aniline & N-methylaniline
(b) Acetaldehyde from Ethanol
Solution: a) Aniline (C6H5-NH2) gives N-H group stretching at about 3400 cm–1
but N-methyl aniline (C6H5-NH-CH3) gives N-H stretching at about 3450 cm–1.
(b) Acetaldehyde gives C = O group stretching at about 1730 cm–1,

while ethanol gives O—H stretching at about 3630 cm–1.
31) Give the approximate characteristics absorption ba nds of C-N group in the IR spectra of
following compounds
(a) C 6 H 5 —NH 2 (b) (C 6 H 5 ) 2 NH (c) (C6H5) 3 N (d) CH 3 —NH 2
a) Solution: : (a) 1340- 1250 cm–1 (b) 1340 – 1280 cm–1 (c) 1360 – 1310 cm–1 (d)
1220 – 1020 cm–1.
SHORT ANSWER QUESTIONS
32) What is the necessary condition for IR spectroscopy?
According to the selection rule for IR transitions, the change in the electric dipole
moment of the functional group present in a molecule or sample during the vibration is
required for a molecule or sample to show an inf rared spectrum.
33) How does the IR spectroscopy instrument work?
The infrared spectroscopy instrumentation is shown below.
First, an IR light beam from the source is split into two and passed through the reference and
sample. Both of these beams are now reflected in order to pass through a splitter and then a

detector. After the processor deciphers the data passed through the detector, the required reading
is printed out.
CHECK POINT 01-02
1) What is the frequency of the mild IR
a) 0.7-2.5µ b) 2.5-50µ c) 50-200µ d) all of the above
2) Which is not use of IR spectroscopy?
a) Functional group b) Structure identify c) A & B both d) metal detecting
3) Which is principal of the IR spectroscopy?
a) Absortion b) Emissions c) Adsorption d) None of this
4) Which is important region in IR spectra?
a) Finger print region b) Functional group region c) A and B both d) None of this
SUMMARY:
The ideas fundamental to an understanding of infrared spectroscopy were intro duced in this
chapter. The electromagnetic spectrum was considered in terms of various atomic and
molecular processes and classical and quantum ideas were introduced. The vibrations of
molecules and how they produce infrared spectra were then examined. The various factors
that are responsible for the position and intensity of infrared modes were described. Factors
such as combination and overtone bands, Fermi resonance, coupling and vibration – rotation
bands can lead to changes in infrared spectra. An appre ciation of these issues is important
whenexamining spectra and these factors were outlined in this chapter. For further
reference, there is a range of books and book chapters available which provide an overview
of the theory behind infrared spectroscopy .Absorption of electromagnetic radiation in
infrared region can cause changes in the vibrational and rotational energy states.A molecule
consisting of n atoms has a total of 3n degrees of freedom. The number of fundamental
vibrational bands in a molecule is equal to the degree of freedom of a molecule however
these numbers of bands is seldom obtained because of the occurrence of certain non -
fundamental bands such as overtones, combinations of fundamental vibrations or difference
of fundamental vibration bands.The IR-spectrum can be obtained in all the three states,
solid, liquid and gas.Fourier-transform infrared spectrometers are superior than the
traditional dispersive spectrometers and gives high resolution spectrum in less time.
KEY WORD
Force Constant, Intramolecular Hydrogen bonding, Nitro Compound, Absorption Region
MOOCS
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=0S_bt3JI150
https://www.youtube.com/watch?v=t5stvnKNXbg

WIKIPEDIA
https://en.wikipedia.org/wiki/Infrared_spectroscopy
https://www.britannica.com/science/infrared-source
OER
____
REFERENCE BOOKS
1. Atkins, P. and de Paula, J., Physical Chemistry, 7th Edn, Oxford University Press,
Oxford, UK, 2002.
2. Vincent, A., Molecular Symmetry and Group Theory, 2nd Edn, Wiley, Chichester,
UK, 2001.
3. Gunzler, H. and Gremlich, H.-U., ¨ IR Spectroscopy: An Introduction, Wiley-VCH,
Weinheim, Germany, 2002
4. Hollas, J. M., Basic Atomic and Molecular Spectroscopy, Wiley, Chichester, UK,
2002
5. Steele, D., ‘Infrared Spectroscopy: Theory’, in Handbook of Vibrational
Spectroscopy, Vol. 1, Chalmers, J. M. and Griffiths, P. R. (Eds), Wiley, Chichester,
UK, 2002, pp. 44–70.
6. Barrow, G. M., Introduction to Molecular Spectroscopy, McGraw -Hill, New York,
1962.
7. Hollas, J. M., Modern Spectroscopy, 3rd Edn, Wiley, Chichester, UK, 1996
8. Fundamentals of molecular spectroscopy; C.N. Banwell, Tata McGraw Hill, New
Delhi.
9. Infrafed spectra of Inorganic and Coordination Compounds; K. Nakamoto; (John
Wiley & Sons, New York)
10. Molecular Spectroscopy, Principles and Chemical applications; P,R singh & S.K.
Dikshit (S.Chand & Co. Ltd., New Delhi)
11. Molecular spectroscopy, P.S. Sindhu; (Tata McGraw Hill, New Dehil)
12. Physical methods in Inorganic Chemistry; R.S. Drago, East West Press Pvt. Ltd.,
New Delhi.

CREDIT 01-UNIT 03: INTRUMENTATION AND APPLICATION: BET
LEARNING OBJECTIVES
 Determine the total surface area of an adsorbent
 State about multilayer adsorption and BET adsorption isotherm
 Explain how BET equation explains various adsorption isotherms
 Describe the principle involved in BET measurements
 Explain the instrumental components and their working
INTRODUCTION
Brunauer–Emmett–Teller (BET) theory: Aims to explain the

physical adsorption of gas molecules on a solid surface and serves as the basis for an
important analysis technique for the measurement of the specific surface area of materials.
The observations are very often referred to as physical adsorption or physisorption. In
1938, Stephen Brunauer, Paul Hugh Emmett, and Edward Teller presented their theory in
the Journal of the American Chemical Society.[1] BET theory applies to systems of
multilayer adsorption that usually utilizes a probing gas (call ed the adsorbate) that do not
react chemically with the adsorptive (the material upon which the gas attaches to and the
gas phase is called the adsorptive) to quantify specific surface area. Nitrogen is the most
commonly employed gaseous adsorbate for probing surface(s). For this reason, standard
BET analysis is most often conducted at the boiling temperature of N 2 (77 K). Other
probing adsorbates are also utilized, albeit less often, allo wing the measurement of surface
area at different temperatures and measurement scales. These include argon, carbon
dioxide, and water. Specific surface area is a scale -dependent property, with no single true
value of specific surface area definable, and th us quantities of specific surface area
determined through BET theory may depend on the adsorbate molecule utilized and its
adsorption cross section.
a)Gas adsorption or Nitrogen adsorption
b) Stephen Brunauer, Paul Hugh Emmett, and Edward Teller.

c) Directly measures surface area &pore size distribution.
d) BET theory deviates from ideal to actual analysis.
01-03-01: BASIC PRINCIPLE

SOLVED PROBLEMS 01
34) The B.E.T. theory was proposed in the year?
a)1940
b)1935
c)1938
d) 1945
35) The B.E.T. theory was based on the ____________
a)Singlelayeradsorption
b)Multilayeradsorption
c)Doublelayeradsorption
d) None of the mentioned
36) How can I get the correct BET measurement with correlation coefficient, r 0.99 and C
constant non –negative?
Ans: I have been trying to get the correct measurement for surface area for a
powder. I made after vacuum drying suspension and then crushing by pestle and

mortar. I did with and crushing too but can’t get any good result s most of the time
the correlation coefficient r is not 0.99 and C constant is negative should the particle
be milled too internal structures of the particles.
37) Which surface area shows best result for porous material: BET surface area or Langmuir
surface area?
Ans: I get two different results on surface of the same sample.
a) BET surface area (linear regression)
b) Langmuir surface area (non linear regression)
But which ane is more correct for porous material. The Langmuir one usually
recommended for mono layer adsorption is not taking i n to account porous
distribution all over the surface area on the solid material.
01-03-02: THE CONCEPT OF THE THEORY IS AN EXTENSION OF THE
LANGMUIR THEORY
The concept of the theory is an extension of the Langmuir theory, which is a theory
for monolayer molecular adsorption, to multilayer adsorption with the following
hypotheses:
1) gas molecules physically adsorb on a solid in layers infinitely;
2) gas molecules only interact with adjacent layers; and
3) the Langmuir theory can be applied to each layer.
4) the enthalpy of adsorption for the first layer is constant and greater than the second (and
higher).
5) the enthalpy of adsorption for the second (and higher) layers is the same as the enthalpy of
liquefaction.
The resulting BET equation is
where c is referred to as the BET C-constant, is the vapor pressure of the

adsorptive bulk liquid phase which would be at the temperature of the adsorbate and
θ is the "surface coverage, defined as:

Here is the amount of adsorbate and is called the monolayer equivalent.
The is the entire amount that would be present as a monolayer (which is
theoretically impossible for physical adsorption)would cover the surface with
exactly one layer of adsorbate. The above equation is usually rearranged to yield the
following equation for the ease of analysis:
where and are the equilibrium and the saturationpressure of adsorbates at the
temperature of adsorption, respectively; is the adsorbed gas quantity (for example, in volume
units) while is the monolayer adsorbed gas quantity. is the BET constant,
where is the heat of adsorption for the first layer, and is that for the second
and higher layers and is equal to the heat of liquefaction or heat of vaporization.
Equation (1) is an adsorption isotherm and can be plotted as a straight line
with on the y-axis and on the x-axis according to

experimental results. This plot is called a BET plot. The linear relationship of this
equation is maintained only in the range of . The value of the
slope and the y-intercept of the line are used to calculate the monolayer
adsorbed gas quantity and the BET constant . The following equations can be
used:
The BET method is widely used in materials science for the calculation of surface
areas of solids by physical adsorption of gas molecules. The total surface area and
the specific surface area are given by
where is in units of volume which are also the units of the monolayer volume of the
adsorbate gas, is the Avogadro number, {displaystyle s} the adsorptioncross section

of the adsorbate, the molar volume of the adsorbate gas, and the mass of the solid
sample or adsorbent.
Determination of surface area of adsorbent:

We know that volume occupied by one mole of an idea gas = 22.414 dm 3
Or, number of molecules occupying 22.414 dm 3 volume = 6.023 × 10 23
Therefore, number of molecules, N, corresponding to 𝑉𝑚𝑜𝑛𝑜 = 𝑉𝑚𝑜𝑛𝑜 /22.414 ×6.023 ×
10 23 (1)
The total surface area of the adsorbent can be obtained if we multiply the above number N
by the area of cross section of a single molecule, A. The latter can be obtained from the
density measurements.
Assuming close packing with negligible void volume, the volume, 𝜈occupied by a single
molecule can be obtained from density ρ, as follows:
ρ = 𝑀/(2)
where, 𝑁𝐴 = Avogadros constant, 6.023 × 10 23
𝑣 = 𝑀/ ρ 𝑁A (3)
If the molecule is assumed to be spherical with radius, r, then,
𝑣 = 4/ 3 𝜋𝑟 3 = 𝑀 /ρ 𝑁𝐴 (4)
r = [3/ 4𝜋x𝑀/ ρ ] 1/3(5)
Therefore, A = 𝜋r 2 = [ 3/ 4𝜋 x 𝑀/ ρ 𝑁𝐴 ] 2/3
(6)
However, the area of cross-section obtained from the above relation (6) is not accurate.
This is because, we have made use of the following approximations:

 We have assumed a close packing, since we do not have the data on the exact
nature of packing of the adsorbate molecules on the surface of the adsorbent.
 The void volume is neglected.
 The adsorbate molecules are assumed to be perfectly spherical, with no
distortions.
The results can be significantly improved if we have detailed knowledge about the crystal
structure.
Emmett and Brunauer made use of the following app roximation to calculate the area of
cross-section of a single molecule: ‘the average cross section of the adsorbate molecules is
the same as that of the molecules in the corresponding plane of closest packing in the
solidified gas’
A = 4 × 0.86 × [ 1/ 4√2 x 𝑀/ ρ 𝑁𝐴 ] 2/3
(7)
Once the value of the area of cross-section of a single molecule is obtained,
The total surface area of the adsorbent = A × N (8)
Multilayer adsorption:
In the Langmuir adsorption, a monolayer forma tion of adsorbate gas molecules on the
surface of the adsorbent is assumed at low pressure and moderately high temperatures. This
assumption, however, is not valid at high pressures and low temperatures. When the gas
pressure is high, greater number of adsorbate molecules strike unit surface area of the
adsorbent in unit time. And when the temperatures are low, the thermal energies of the gas
molecules are low, insufficient to overcome the Van der waals forces of attraction between
the adsorbed molecules and the surrounding unadsorbed molecules. As a result of these two
effects, the solid adsorbent holds on many layers of gas molecules on to its surface,
resulting into what is called as a multilayer adsorption. Multilayer adsorption is especially
prevailant at gas pressures close to gas saturation pressure, at a particular temperature .
SOLVED PROBLEMS 02
38) Which of the following is an assumption for B.E.T theory?
a) The solid surface possess uniform, localised sites
b) The adsorption at one site does not affect adsorption at neighbouring site
c) Physical adsorption of adsorbate occurs resulting in the formation of multilayers
d) All of the mentioned
39) The energy of adsorption in the first layer is ___________
a)Increasing
b)Decreasing
c)Constant
40) How to prepate a photocatalyst with both good crystallinity and large BET surface area?

Is it possible to improve the crustallinity of photocatalyst be calcinations without
decteasing the BET surface area of a photocat alys t or even increase the BET surface
area? Hydrothermal synthesis you can could try go and something else. Or just prepare
some MOFs/COFs. No it is not possible. Ostwald ripening effect will make your
particles bigger with increasing temperature
41) Can anyone tell me what is the degassing temperature for the BET analyss of copper
sultide (Cus) powder?
Ans: The degassing of the sample is carried out before the BET measurement. I want
to know how much degassing time and temperature to perform on my sample. It
depends on the stability of your material as said by Eric Aguilar Garcia. You can
verify it through TGA analysis. For my sample (Mof and MOF composit) I prefer
degassing at 120-150 2 C for 12 hours.
01-03-03: METHODOLOGY AND EXPERIMENTAL PROCEDURE

The various types of apparatus used for the determination of physisorption isotherms may
be divided into two groups, depending on: (a) measurement of the amount of gas removed
from the gas phase (i.e., manometric methods) and (b) direct measurement of the uptake of
gas (i.e., gravimetric measurement of the change in mass of the adsorbent). In practice,
static or dynamic techniques may be used in either case. As mentioned in Section 2, the
surface excess amount is the quantity experimentally determined. For the adsorp tion of
vapours below 100 kPa (1 bar) (e.g., N2 , Ar, Kr adsorption at cryogenic temperatures) the
surface excess amount and the total amount adsorbed can be considered to be essentially
identical.
A static manometric determination entails the measurement of changes of pressure of

calibrated gas volumes: a known amount of pure gas is admitted to a confined, calibrated
volume containing the adsorbent, which is maintained at constant temperature. As
adsorption takes place, the pressure in the confined volume falls until equilibrium is
established. The amount of gas adsorbed at the equilibrium pressure is given as the
difference between the amount of gas admitted and the amount of gas required to fill the
space around the adsorbent, i.e., the dead space. The ad sorption isotherm is usually
constructed point-by-point by admission of successive charges of gas to the adsorbent with
the aid of a dosing technique and application of the appropriate gas laws. The volume of the
dead space must, of course, be known accurately: it is obtained either by pre-calibration of
the confined volume and subtracting the volume of the adsorbent (calculated from its
density or by the admission of a gas which is adsorbed to a negligible extent). It is
important to understand that the determination of the dead space usually accounts for the
largest element of uncertainty in the total error inventory of the measured adsorbed amount.

A ‘continuous’ procedure can be used to construct the isotherm under quasi -equilibrium
conditions: the pure adsorptive is admitted to (or removed from) the system at a slow and
constant rate and a manometric or gravimetric technique used to follow the variation of the
amount adsorbed with increase (or decrease) in pressure. In such measurements involving
gas flow it is essential to confirm that the results are not affected by change in flow rate
and to check the agreement with representative isotherms determined by a static method.
Two different carrier gas techniques may be employed to study the amount adsorbed.
Inverse gas chromatography, which involves an elution phenomenon and the determination
of a retention time, is mainly applied for studies in the low monolayer coverage (or
micropore filling) region, although it has been used, apparently satisfactorily, up to
monolayer coverage [2]. Adsorption/desorption under carrier gas (i.e., the Nelson and
Eggertsen flow method [4]) also allows one to construct an adsorption/desorption isotherm,
but this technique is frequently only applied for a single point surface ar ea assessment.
Both techniques require that the adsorption of the carrier gas be negligible.

SOLVED PROBLEMS 03
42) The surface area available for the nth layer is equal to the coverage of ____________
a)(n-1)thlayer
b)(n+1)thlayer
c)nthlayer
d) none of the mentioned
43) In the B.E.T. equation, what does p 0 denotes?

a) Pressure of the gas molecules
b) Unsaturated vapor pressure of the gas molecules
c) Saturated vapor pressure of the gas molecules
d) All of the mentioned
44) What is degassing in BET?
Ans. To select degassing conditions for different materials you need to knew the
peculiarities of your samples.
I.If the material has low thermal stability you can use only low temperature
and a vaccum for degassing.
II. If the materials porous structure consists of channels with of micro porous
dimension you need to degas it for a long time period.
III. In general you must take to attention lite value data concerning similar
material investigations.
45) What conditions can cause the specific area to decrease with decreasing crystallite size?
Ans: The considering the relation between crystallite size and BET specific surface area
for nanoparticles. We know that specific surface area increases with decreasing
crystallite size (Smaller) crystallite size higher SSA.
01-03-04: APPLICATIONS
CEMENT AND CONCRETE :
The rate of curing of concrete depends on the fineness of the cement and of the components used
in its manufacture, which may include fly ash, silica fume and other materials, in addition to
the calcinated limestone which causes it to harden. Although the Blaine air permeability
method is often preferred, due to its simplicity and low cost, the nitrogen BET method is also
used.
When hydrated cement hardens, the calcium silicate hydrate (or C-S-H), which is responsible for
the hardening reaction, has a large specific surface area because of its high porosity. This porosity
is related to a number of important properties of the material, including the strength and
permeability, which in turn affect the properties of the resulting concrete. Measurement of
the specific surface area using the BET method is useful for comparing different cements. This
may be performed using adsorption isotherms measured in different ways, including the
adsorption of water vapour at temperatures near ambient, and adsorption of nitrogen at 77 K (the
boiling point of liquid nitrogen). Different methods of measuring cement paste surface areas often
give very different values, but for a single method the results are still useful for comparing
different cements.
ACTIVATED CARBON:
Activated carbon has strong affinity for many gases and has an adsorption cross
section displaystyle{s} of 0.162 nm2 for nitrogen adsorption at liquid-nitrogen temperature

(77 K). BET theory can be applied to estimate the specific surface area of activated carbon from
experimental data, demonstrating a large specific surface area, even around 3000 m2/g. However,
this surface area is largely overestimated due to enhanced adsorption in micropores, and more
realistic methods should be used for its estimation, such as the subtracting pore effect (SPE)
method.
Catalysis:

In the field of solid catalysis, the surface area of catalysts is an important factor in catalytic
activity. Inorganic materials such as mesoporous silica and layered clay minerals have high
surface areas of several hundred m2/g calculated by the BET method, indicating the possibility of
application for efficient catalytic materials.
This procedure is based on the following main criteria: (a) the quantity C should be posi tive
(i.e., a negative intercept on the ordinate of the BET plot is the first indication that one is
outside the appropriate range); (b) application of the BET equation should be restricted to
the range where the term n(1 – p/p0) continuously increases with p/p0 ; (c) the p/p0 value
corresponding to nm should be within the selected BET range. It must be re -emphasised
that this procedure should not be expected to confirm the validity of the BET monolayer
capacity. Thus, the BET-area derived from a Type I isotherm must not be treated as a
realistic probe accessible surface area. It represents an apparent surface area, which may be
regarded as a useful adsorbent “fingerprint”
 Surface area analysis of solid materials (such as carbon black, catalysts, batteries and
ceramics)
 Simultaneous acquisition of surface area and pore size data.
 Non-destructive method.
SOLVED PROBLEMS 04
46) According to B.E.T. equation, the plot of P/V(P 0 -P) versus P/P 0 will yield a
____________
a)Straightline
b)Parabola
c)Hyperbola
d) Eclipse
47) The B.E.T. theory is used in calculating the ____________
a)Surfaceareaofadsorbate
b)Surfaceareaofadsorbentonly
c)Surfaceareaofadsorbentsandcatalyst

48) How to perform BET analysis of MoF?
Ans. I have synthesized Michel MoF using the micro wave irradiation technique.
However, I am unable to get the surface area of the material both mesoporous and
microporous synthesis. It will be better if you find out a method that reported in the
article and follow the procedure I guess after degassing was you MoF still stable at
that circumstance.
49) What are the materials having BET surface area higher than 2000 mz/g?

Ans. The searching to find the list of different materials having surface areas higher
than 2000 mz/g. Kindly share the name of the material its BET surface area with the
DOI link Newly reported materials having high surface areas MoF and CoFs.
CHECK POINT
1) THE SURFACE AREA OCCUPIED BY A SINGLE GAS MOLECULE IS INVERSELY

PROPORTIONAL TO THE ____________
2) THE TOTAL SURFACE AREA COVERED BY ALL THE MOLECULES OF THE
ADSORBED GAS IS GIVEN BY ____________
SUMMARY
Brunauer–Emmett–Teller (BET) theory is used to measure the surface area of solid or
porous materials. It gives important information on their physical structu re as the area of a
material’s surface affects how that solid will interact with its environment. Many properties
such as dissolution rates, catalytic activity, moisture retention, and shelf life are often
correlated to a material’s surface area. Critical to the design and manufacture of solids,
surface area analysis is one of the most widely used methods in material characterization .
To determine the pore volume and pore size distribution, the gas pressure is increased
further incrementally until all pores are filled with nitrogen molecules. Next, the gas
pressure is reduced incrementally, evaporating the condensed nitrogen gas from the system.
Evaluation of the adsorption and desorption isotherms reveals information about the pore
volume and pores size distribution.
KEY WORDS
Adsorbate, isothermal ,Adsobent, kinetics, thermodynamics, Avogadros number, molar
Volume
ANSWER TO CHECK POINT

1) Density of the liquefied gas
2) S = nβN A
MOOCS
____
YOUTUBE VIDEOS
https://mercer-instruments.com/en/applications/BET-surface-area-analysis.html
https://www.youtube.com/watch?v=VfxNYAfFho4
WIKIPEDIA
https://en.wikipedia.org/wiki/BET_theory
https://www.iitk.ac.in/che/pdf/resources/BET-TPX-Chemi-reading-material.pdf
OER
____

REFERENCE BOOKS
[1] K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. Pieroti, J. Rouquerol, T.
Siemieniewska. Pure Appl. Chem. 57, (1985)
[2] J. Rouquerol, F. Rouquerol, K. S. W. Sing, P. Llewellyn, G. Maurin. Adsorption by
Powders and Porous Solids: Principles, Methodology and Applications, Academic Press
(2014).
[3] E. R. Cohen, T. Cvitas, J. G. Frey, B. Holmström, K. Kuchitsu, R. Marquardt, I. Mills,
F. Pavese, M. Quack, J. Stohner, H. L. Strauss, M. Takami, A. J. Thor. Quantities, Units and
Symbols in Physical Chemistry, 3rd ed., RSC Publishing, Cambridge, UK (2007).
[4] S. Lowell, J. Shields, M. A. Thomas, M. Thommes, Characterization of Porous Solids
and Powders: Surface Area. Porosity and Density, Springer, 2004
[5] J. Silvestre-Albero, A. M. Silvestre-Albero, P. L. Llewellyn, F. Rodriguez-Reinoso. J.
Phys. Chem. C 117, 16885 (2013).
[6] M. Thommes, K. A. Cychosz. Adsorption 20, 233 (2014).

CREDIT 01-UNIT 04: PRINCIPLES AND APPLICATIONS OF XRD
LEARNING OBJECTIVES
 Explain Powder X-ray Diffracion
 State Bragg’s Law of Diffraction
 State applications of Powder XRD
 State Strengths and Limitations of X-ray Powder Diffraction
INTRODUCTION
X-ray diffraction is now a common technique for t he study of crystal structures and atomic
spacing. X-ray diffraction is based on constructive interference of monochromatic X -rays
and a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to
produce monochromatic radiation, collimated to concentrate, and directed toward the
sample (Figure 1).
The interaction of the incident rays with the sample produces constructive interference (and
a diffracted ray) when conditions satisfy Bragg’s law:
where n is an integer, λ is the wavelength of the X-rays, d is the interplanar spacing

generating the diffraction, and u is the diffraction angle.
This law relates the wavelength of electromagnetic radiation to the diffraction angle and the
lattice spacing in a crystalline sample. These diffract ed X-rays are then detected, processed,
and counted. By scanning the sample through arange of 2u angles, all possible diffraction
directions of the lattice should be attained due to the random orientation of the powdered
material. Conversion of the diffraction peaks to d-spacings allows identification of the
compound because each compound has a set of unique d -spacings. Typically, this is
achieved by comparison of d-spacings with standard reference patterns.
01-04-01: PRINCIPLES
X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and
an X-ray detector .

X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the t arget
material with electrons. When electrons have sufficient energy to dislodge inner shell
electrons of the target material, characteristic X -ray spectra are produced. These spectra
consist of several components, the most common being Ka and Kb.
Ka consists, in part, of Ka1 and Ka2. Ka1 has a slightly shorter wavelength and twice the
intensity of Ka2. The specific wavelengths are characteristic of the target material (Cu, Fe,
Mo, Cr). Filtering, by foils or crystal monochrometers, is required to produce
monochromatic X-rays needed for diffraction. Ka1 and Ka2 are sufficiently close in
wavelength such that a weighted average of the two is used. Copper is the most common
target material for single-crystal diffraction, with CuKa radiation D 1.5418 A . These X -
rays are collimated and directed onto the sample. As the sample and detector are rotated,
the intensity of the reflected X-rays is recorded. When the geometry of the incident X -rays
impinging the sample satisfies Bragg’s law, constructive interference occ urs and a peak in
intensity appears. A detector records and processes this X -ray signal and converts the signal
to a count rate, which is then output to a device such as a printer or computer monitor.
The geometry of an X-ray diffractometer is such that the sample rotates in the path of the
collimated X-ray beam at an angle u while the X-ray detector is mounted on an arm to
collect the diffracted X-rays and rotates at an angle of 2u. The instrument used to maintain
the angle and rotate the sample is termed a goniometer.
For typical powder patterns, data are collected at 2u from 5 to 70, angles that are preset in
the X-ray scan. X-ray powder diffraction is most widely used for the identification of
unknown crystalline materials (e.g., minerals, inorganic co mpounds). Determination of
unknown solids is critical to studies in geology, environmental science, material science,
engineering, and biology. Other applications include charact erization of crystalline
materials, identification of fine-grained minerals such as clays and mixed layer clays that
are difficult to determine optically, determination of unit cell dimensions, and measurement

of sample purity. With specialized techniques, X -ray diffraction (XRD) can be used to
determine crystal structures by using Rietveld refinement, determine modal amounts of
minerals (quantitative analysis), characterize thin film samples, and make textural
measurements, such as the orientation of grains, in a polycrystalline sample (Brindley and
Brown, 1980).
Powder X-ray diffraction (PXRD) is perhaps the most widely used analytical technique for
characterizing materials. As the name suggests, the sample is usually in a powdery form,
consisting of fine grains of single crystalline material to be studied. The technique is also
used widely for studying particles in liquid suspensions or polycrystalline solids (bulk or
thin film materials).
The term 'powder' really means that the crytalline domains are randomly oriented in the
sample. Therefore when the 2-D diffraction pattern is recorded, it shows concentric rings of
scattering peaks corresponding to the various d spacings in the crystal lattice.
The positions and the intensities of the peaks are used for identifying the underlying
structure (or phase) of the material. For example, the diffraction lines of graphite would be
different from diamond even though they both are made of carbon atoms. This phase
identification is important because the material properties are highly dependent on structure
(just think of graphite and diamond).
Powder diffraction data can be collected using either reflection or transmission geometry,
as shown below.

Because the particles in the powder sample are randomly oriented, these two methods will
yield the same data.
A powder XRD scan typically represents a plot of scattering intensity v/s. the scattering
angle 2θ or the corresponding d-spacing. The peak positions, intensities, widths and shapes
all provide important information about the structure of the material.
The diffraction from ideal crystalline substances are characterized by well defined Bragg
peaks in X-ray diffraction. The crystalline substances have long range order. The
amorphous substances do not possess this long range order. So the diffraction from them do
not show sharp Bragg peaks. In amorphous phase, X-rays will be scattered in many
directions leading to a large bump distributed in a wide range (2θ) instead of high intensity
narrower peaks.
Max von Laue, in 1912, discovered that crystalline substances act as three -dimensional
diffraction gratings for X-ray wavelengths similar to the spacing of planes in a crystal
lattice. X-ray diffraction is based on constructive interference of monochromatic X -rays
and a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to
produce monochromatic radiation, collimated to concentrate, and directed toward the
sample. In principle, X-ray diffractometers consist of three basic elements: an X -ray tube, a
sample holder, and an X-ray detector.

The X-ray wavelengths are characteristic of the target mat erial (Cu, Fe, Mo, Cr). Filtering,
by foils or crystal monochrometers, is required to produce monochromatic X -rays needed
for diffraction. Kα1 and Kα2 are sufficiently close in wavelength such that a weighted
average of the two is used. Copper is the most common target material for single-crystal
diffraction, with CuKα radiation = 1.5418 Å. These X -rays are collimated and directed onto
the sample. As the sample and detector are rotated, the intensity of the reflected X -rays is
recorded. When the geometry of the incident X-rays impinging the sample satisfies the
Bragg Equation, constructive interference occurs and a peak in intensity occurs. A detector
records and processes this X-ray signal and converts the signal to a count rate which is then
output to a device such as a printer or computer monitor.
The interaction of the incident rays with the sample produces constructive interference (and
a diffracted ray) when conditions satisfy Bragg's Law. This law relates the wavelength of
electromagnetic radiation to the diffraction angle and the lattice spacing in a crystalline
sample. These diffracted X-rays are then detected, processed and counted. By scanning the
sample through a range of 2θ angles, all possible diffraction directions of the lattice should
be attained due to the random orientation of the powdered material. Conversion of the
diffraction peaks to d-spacings allows identification of the material because each material

has a set of unique d-spacings. Typically, this is achieved by comparison of dspacings with
standard reference patterns.
The geometry of an X-ray diffractometer is such that the sample rotates in the path of the
collimated X-ray beam at an angle θ while the X-ray detector is mounted on an arm to
collect the diffracted X-rays and rotates at an angle of 2θ. The instrument used to maintain
the angle and rotate the sample is termed a goniometer. For typical powder patterns, data is
collected at 2θ from ~5° to 70°, angles that are preset in the X -ray scan.
There are some strengths and some limitations of X -ray powder diffraction (XRPD):
a) Strengths:
 Powerful and rapid (<20 min) for identification of an unknown mineral.
 Provides unambiguous mineral determination in most cases.
 Requires minimal sample preparation.
 Wide availability of XRD units.
 Relatively straightforward data interpretation.
b) Limitations:
 Homogeneous and single-phase material is best for identification of an unk.
 Access to a standard reference file of inorganic compounds is required.
 Material, in tenths of a gram quantity, must be ground into a powder.
 For mixed materials, detection limit is » 2% of sample.
 For unit cell determinations, indexing of patterns for nonisometric crystal systems is
complicated.
 Peak overlay may occur and worsens for high angle “reflections”.

X-ray diffraction is a high-tech, nondestructive technique for analyzing a wide range of
materials including fluids, metals, minerals, polymers, catalysts, plastics, pharmaceuticals,
thin-film coatings, ceramics, solar cells, and semiconductors. The technique finds
innumerable practical applications in various industries, including microelectronics, power
generation, aerospace, and many more. XRD analysis can easily detect the existence of
defects in a particular crystal, its resistance level to stress, its texture, its size and degree of
crystallinity, and virtually any other variable relating to the sample’s basic structure.
The objective of this review is to present the new developments in applications of XRD in
different analysis, covering the period between 2009 and 2014. It is useful to give a short
introduction to the concept of the XRD, some characteristics of the instruments used, and
sample preparation. Quantitative and qualitative determination in different fields of
analysis using this technique will be presented.
SOLVED PROBLEMS 01
50) If the atomic numbers of the zirconium, molybdenum, palladium and tin are 40,42,46
and 50 respectively, the suitable filter for x -radiation from molybdenum is
(A) Zirconium
(B) Palladium
(C) Tin
(D) All of the above
51) Filters used in XRD may eliminate
(A) K α1
(B) K β
(C) K α2

52) What do you understand by x-ray diffractometry?
X-ray diffractometry is a versatile technique for characterization of crystalline andsemi -
crystalline materials. It provides a wealth of infor mation on crystal structures, phases,
texture, crystal defects and strain .It is based on constructive interference of abeam of
x-rays diffracted at different angles from each set of atomic planes withinthecrystal
lattice. The technique serves to fingerprint a material on the basis of
periodicarrangement of atoms within the crystal lattice.
53) What is the basic law governing diffraction of x -rays?
The diffraction of x-rays results in the constructive interference when conditions of
Braggs law are fulfilled. The law states nλ =2d Sinθ where n is an integer, λ is the
wavelength of incident x-ray beam, d is the interplanar separation between the atomic
layers of the crystal and θ is the angle of diffraction. The diffracted rays are led to the
detector to form a pattern or a diffractogram.

01-04-02: INTRUMENTATION
Xrd Theoretical Aspects: Ways to prepare a powder sample
The instrumentation that is used for powder diffraction measurements has not changed
much from that developed in the late 1940s. The major differ ence found in modern
instrumentation is the use of the minicomputer for control, data acquisition, and data
processing. Figure 2 illustrates the geometry of the system, showing the layout of a typical
diffractometer with system source F, Soller slits P and RP, sample S, divergence slit D, and
receiving slit R. The axis of the goniometer is at A.
This geometric arrangement is known as the Bragg-Brentano parafocusing system and is

typified by a diverging beam from a line source F, falling onto the specimen S, being
diffracted and passing through a receiving slit R to the detector. Distances FA and AR are
equal. The amount of divergence is determined by the effective focal width of the source
and the aperture of the divergence slit D. Axial divergence is cont rolled by two sets of
parallel plate collimators (Soller slits) P and RP placed between focus and specimen and
between specimen and scatter slit, respectively. Use of the narrower divergence slit will
give smaller specimen coverage at a given diffraction a ngle, thus allowing the attainment of
lower diffraction angles where the specimen has a larger apparent surface (thus larger
values of d are attainable). This is achieved, however, only at the expense of intensity loss.
Choice of the divergence slit, plus its matched scatter slit, is thus governed by the angular
range to be covered. The decision as to whether or not the slit size should be increased at a
given angle will be determined by the available intensity. A photon detector, typically a
scintillation detector, is placed behind the scatter slit and converts the diffracted X -ray
photons into voltage pulses. These pulses may be integrated in a rate meter to give an
analog signal on an x/t recorder. By synchronizing the scanning speed of the goniometer
with the recorder, a plot of degrees 2u versus intensity, called the diffractogram, is
obtained.

A timer/scaler is also provided for quantitative work and is used to obtain a measure of the
integrated peak intensity of a selected line(s) from each analyte pha se in the specimen. A
diffracted beam monochromator may also be used in order to improve signal -to-noise
characteristics. The output from the diffractometer is a “powder diagram,” essentially a plot
of intensity as a function of diffraction angle, which ma y be in the form of a strip chart or a
hard copy from a computer graphics terminal (Brindley and Brown, 1980).
The powder method derives its name from the fact that the specimen is typically in the form
of a microcrystalline powder, although, as has been i ndicated, any material that is made up
of an ordered array of atoms will give a diffraction pattern. The possibility of using a
diffraction pattern as a means of phase identification was recognized by 1935, but it was
not until the late 1930s that a systematic means of unscrambling the superimposed
diffraction patterns was proposed by Hanawalt, Rinn, and Frevel (1986).
Sample Preparation:
Proper sample preparation is one of the most important requirements in the analysis of
powder samples by X-ray diffraction. This statement is especially true for soils and clays
that contain finely divided colloids, which are poor reflectors of X -rays, as well as other
types of materials such as iron oxide coatings and organic materials that make
characterization by XRD more difficult.
Important factors in sample preparation are:
 Sample properties also influence the quality of a powder pattern by either reducing
intensities or distorting intensities.
 Preferred orientation or texture: Texture means that the powder particles do not
have an arbitrary shape but a strongly regular anisotropic shape, typically platelets
or needles. On preparation these are then preferably oriented along the sample
surface massively changing the peak intensities. Several techniques may be
employed to minimize this effect:
 The most efficient way is to form a slurry in a highly viscous liquid such as nail
varnish. In such a liquid, the random orientation is retained on drying.
 Alternatively, the anisotropic particle shape can be reduced by g rinding in a ball
mill. This should be done with great care as excessive grinding can easily break
down the particle size to nanometer size and lead to amorphization. It is
recommended to try the effect of subsequent 5 min grinding intervals to optimize
the process on respective samples. In the case of coatings or thin films preferred
orientation is often a desired effect. In this case Rietveld refinement can be used to
determine the degree of texture.
 Crystallite size and strain: the broadness of a diffraction peak corresponds to the
mean crystallite size in a reciprocal manner. The smaller the average crystallite

size, the broader the reflections and the lower the absolute intensities. This effect
becomes visible below an average crystallite size of less t han 200 nm. Related to
crystallite size broadening is strain broadening. Strain broadening occurs due to the
presence of defects in crystals. Such strain can be introduced by substitution of
constituting atoms but also by special thermal treatment. It is p ossible to distinguish
strain broadening from size broadening as the angle dependence is much larger than
in the latter case (He, 2009).
 Sample preparation height: Rotating sample holders improve the measurement
statistics and thus provide the best results . However, they are not available for all
machines. The most serious error during sample preparation is to fill the sample
holder too high or too low. Both result in a significant shift of peak positions, which
can make the interpretation difficult.
 Top-loading a bulk powder into a well: 1) Deposit powder in a shallow well of a
sample holder. Use a slightly rough flat surface to press down on the powder,
packing it into the well. 2) Using a slightly rough surface to pack the powder can
help minimize preferred orientation. 3) Mixing the sample with filler such as flour
or glass powder may also help minimize preferred orientation. 4) Powder may need
to be mixed with a binder to prevent it from falling out of the sample holder 5)
Alternatively, the well of the sample holder can be coated with a thin layer of
Vaseline.
 Dispersing a thin powder layer on a smooth surface: 1) A smooth surface such as a
glass slide or a Zero Background Holder (ZBH) may be used to hold a thin layer of
powder.a) glass will contribute an amorphous hump to the diffraction pattern.b) the
ZBH avoids this problem by using an off -axis cut single crystal.2) Dispersing the
powder with alcohol onto the sample holder and then allowing the alcohol to
evaporate, often provides a nice, even coating of powder that will adhere to the
sample holder. 3) Powder may be gently sprinkled onto a piece of double -sided tape
or a thin layer of Vaseline to adhere it to the sample holder. a) The double -sided
tape will contribute to the diffraction pattern. 4) Thes e methods are necessary for
mounting small amounts of powder. 5) These methods help alleviate problems with
preferred orientation. 6) The constant volume assumption is not valid for this type
of sample, and so quantitative and Rietveld analysis will requir e extra work and
may not be possible.
 Important characteristics of samples for XRPD: 1) A flat plate sample for XRPD
should have a smooth flat surface If the surface is not smooth and flat, X -ray
absorption may reduce the intensity of low angle peaks. Para llel-beam optics can be
used to analyze samples with odd shapes or rough surfaces 2) Densely packed 3)

Randomly oriented grains/crystallites 4) Grain size less than 10 microns infinitely
thick
SOLVED PROBLEMS 02
54) X-rays are generated by
(A) Geiger tube
(B) Goniometer
(C) Coolidge tube
(D) Rotameter
55) Collimators used in XRD are made up of
(A) Thin quartz tube
(B) Thin glass plates
(C) Thin metal plates
56) Explain the basic configuration of an XRD system
X-ray diffractometer consists of three basic components – an x-ray source or tube,
sample holder and an x-ray detector. X-rays are generated by targeting a metal cathode
block with electrons havingsufficient energy from a heated filament.The electrons
having sufficient energydislodge inner shell electrons of the target material to produce
characteristic x-rays. hese rays are collimated and directed to the sample stage which
holds the specimensample. The diffracted rays are directed to the detector which
converts the x-raysignal to counts which are recorded electronically.
57) List out some advantages of XRD technique
XRD is a material characterization technique which provides a wealth of
informationon material properties and serves as a fingerprint for identificati on of the
material under investigation. The specific advantages of the technique are that it
isnon-destructive and sample can be reused for other confirmatory tests. It is a rapid
technique which takes about 15 to 20 minutes to run a diffracto gramand requires
minimum sample preparation and offers ease of comparison of results with
availabledata bases.
01-04-03: APPLICATIONS I
X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials (e.g. minerals, inorganic compounds). Determination of unknown solids is critical
to studies in geology, environmental science, material science, engineering and biology.
Other applications include:
• characterization of crystalline materials
• identification of fine-grained minerals such as clays
• determination of unit cell dimensions
• measurement of sample purity
With specialized techniques, XRD can be used to:
• determine crystal structures using Rietveld refinement

• determine the amounts of minerals (quantitative analysis)
• characterize thin films samples by: o determining lattice mismatch between film
and substrate and to inferring stress and strain o determining dislocation density
and quality of the film by rocking curve measurements o measuring super
lattices in multilayered epitaxial structures o determining the thickness,
roughness and density of the film using glancing incidence X -ray reflectivity
measurements
• make textural measurements, such as the orientation of grains, in a
polycrystalline sample.
a) Pharmaceutical Industry:
The pharmaceutical industry is one of the most successful in the technology sector,
and its ability to innovate has seen it launch nearly 1,400 new chemical entities as
human therapeutics over the past 30 years. Despite this success, the research and
development (R&D) process to bring a drug successfully to market remains
challenging. Drug development is a risky and expensive process in order to increase
demand for more available and affordable drugs (generic drugs) and to propose
adapted new drug products. In the drug design, discovery, development, and
formulation process, X-ray powder diffraction can help to establish a formulation by
discovering the morphology and the degree of crystallinity, providing unique
polymorph identification, and determining the quantity of each in mixture. With
XRD, nonambient analysis can also be performed to study moisture influence on
physical properties of drugs.
Drugs come in a variety of forms (tablets, pills, capsules, aerosol sprays) and with a
variety of formulations. A single drug may be formulated in dozens of ways to
enhance the ability of the drug to enter the body (fast action or long -lasting action)
and be delivered to a targeted area (skin cream, nasal spray, anti -itch, anticancer). A
formulation could help shelf life, provide buffering capability in the stomach, make
the medicine taste better, or be part of a design for time release of the drug into the
blood stream. The first question to ask is what problem are you trying to solve? Do
you want to identify the ingredients or understand the effectiveness of a drug
coating or packaging material? Are you trying to determine effective shelf life? X -
ray diffraction analyses are used in all these applications. XRD can be used to
unambiguously characterize the composition of pharmaceu ticals. An XRD pattern is
a direct result of the crystal structures that are present in the pharmaceutical under
study. As such, the parameters typically associated with crystal structure can be
simply accessed. For example, once an active drug has been is olated, an indexed X-
ray powder diffraction pattern is required to analyze the crystal structure, secure a
patent, and protect the company’s investment. For multi component formulations,

the actual percentages of the active ingredients in the final dosage form can be
accurately analyzed in situ, along with the percentage of any amorphous packing
ingredients used.
XRPD continues to be an indispensable analytical technique supporting a wide
variety of pharmaceutical development activities. XRD has a broad ran ge of
applications in various stages of drug development and manufacturing, such as
active pharmaceutical ingredient (API) characterization and identification. API
characterization is more commonly applied during drug development, while API
identification is directed more towards manufacturing, regulatory aspects, and
intellectual property. Solid form screening, the activity of generating and analyzing
different solid forms of API, has become an essential part of drug development. The
multistep screening process needs to be designed, performed, and evaluated
carefully, since decisions made based on the screening may have consequences on
the whole life cycle of a pharmaceutical product. The selection of the form for
development is made after solid form screening. The selection criteria include not
only pharmaceutically relevant properties, such as therapeutic efficacy and
processing characteristics, but also intellectual property (IP ) issues . Basic
principles of solid form screening are reviewed, including th e methods used in
experimental screening (generation, characterization, and analysis of solid forms,
data mining tools, and high-throughput screening technologies) as well as basics of
computational methods. Differences between solid screening strategies b etween
brand and generic pharmaceuticals by various manufacturers are dis cussed by
Aaltonen et.
Solid form screening is commonly performed to find a candidate with optimal
properties for early development or to find a form with different properties to
improve a formulation in later development. A variety of screens can be performed
including polymorph, salt, co-crystal, amorphous, and amorphous dispersion. XRPD
is commonly used at various stages of screening to identify and characterize new
forms. It is also used to help evaluate other properties, such as physical stability and
manufacturability, in order to choose the best form for development (Newman,
2011). The author discusses the use of XRPD during screening and form selection of
pharmaceutical materials.
Solid phase transitions such as polymorph interconversions are routinely examined
by XRPD using variable temperature sample stages (VT-XRPD). Both sub-ambient
and elevated temperature stages are available. While thermal techniques such as
differential scanning calirometry (DSC) and thermogravimetric analysis (TGA) are
also widely used for these studies, VT-XRPD permits the direct identification of
crystalline phase as a function of temperature. Most pharmaceutical laboratories rely

on both technologies. Indeed, instruments are available that permit simultaneous
XRPD and DSC sample analyses .
Recent advances in the performance of XRPD instrumentation (particularly with
respect to peak resolution) permit the use of data obtained from conventional
laboratory diffractometers. In addition, the development of direct -space methods for
structure solution require only that the XRPD peak shape and width functions of the
XRPD patterns be accurately defined (Harris, 2012). These techniques were also
applied to obtain crystal structures for three out of five polymorphs of m -
aminobenzoic acid (Williams et al., 2012). Given the importance of the phenomenon
of polymorphism from both fundamental and applied perspectives, there is
considerable interest in the discovery of ne w systems that exhibit abundant
polymorphism. The preparation strategies and structural properties of three new
polymorphs of m-aminobenzoic acid (m-ABA) were reported, elevating this system
to the rare class of polymorphic systems with at least five known polymorphs. The
crystal structures of the three new polymorphs were determined directly from
powder X-ray diffraction data, using the directspace genetic algorithm technique for
structure solution followed by Rietveld refinement, demonstrating the opportu nities
that now exist for determining crystal structures when crystals of sufficient size and
quality for single-crystal X-ray diffraction are not available. The assignment of the
tautomeric form in each polymorph was confirmed by X -ray photoelectron
spectroscopy.
b) Forensic Science:
Chemical analysis of forensic “specimens” usually means identification and/or
comparison. However, the specimens differ from most of those encountered in other
situations in that they constitute evidence, and as such should be pr eserved. Powder
diffraction is a nondestructive process, and is therefore well suited to forensic
analysis. It is also versatile and can be used for analyzing organic, inorganic, and
metallic specimens, and, qualitatively and quantitatively, mixtures of th ese
materials.
A prime example of its value is in the analysis and comparison of street narcotics seizures,
which, in addition to the drug itself, will invariably contain excipients or adulterants. Some
of these compounds will have been added deliberately by the dealer in order to render the
drugs more palatable and of course to maximize profit. In doing so, however, he is creating
an analytical “signature” or profile that can be useful in tracing individual drug seizures to
a common source—the dealer. The more chemical components identified in an individual
seizure, the greater the evidential value of a match between numbers of chemically identical
seizures. In addition, many drugs, and certain excipients or adulterants, exist in different
polymorphic forms, hydrated forms, and optically active or racemic forms, and each

variation may be successfully differentiated by powder diffraction, adding to the evidential
value of the analysis. The opium poppy Papaver somniferum is the source of the narcotic
analgesics morphine and codeine. Salutaridine reductase (SalR; EC 1.1.1.248) reduces the
C-7 keto group of salutaridine to the C-7 (S)-hydroxyl group of salutaridinol in the
biosynthetic pathway that leads to morphine in the opium poppy plant. P. somniferum SalR
was overproduced in Escherichia coli and purified using cobalt -affinity and size-exclusion
chromatography. Hexagonal crystals were obtained using ammonium sulfate as precipitant
and diffracted to a resolution of 1.9 A (Higashi et al., 2010)
Powder X-ray diffraction (PXRD) is used widely in forensic science laboratories with the
main focus on qualitative phase identification and validation of PXRD in the field of
forensic sciences. According to the standard EN ISO/IEC 17025, the method has to be
tested for several parameters. Trueness, specificity, and selectivity of PXRD were tested
using certified reference materials or a combination thereof. All three tested parameters
showed the secure performance of the method. Sample preparation errors were simulated to
evaluate the robustness of the method. These errors were either easily detected by the
operator or non significant for phase identification. In case of the detection limit, a
statistical evaluation of the signal -to-noise ratio showed that a peak criterion of three sigma
is inadequate, and recommendations for a more realistic peak criterion are given .
The uniqueness and limited amounts of forensic samples and samples from objects of
cultural heritage together with the complexity of their composition require the application
of a wide range of micro analytical methods that are nondestructive to the samples, because
these must be preserved for potential later revision. Laboratory powder X -ray micro-
diffraction (micro-XRD) is a very effective nondestructive technique for direct phase
analysis of samples smaller than 1 mm containing crystal constituents. It complements
optical and electron microscopy with elemental microanalysis, especially in cases of
complicated mixtures containing phases with similar chemical co mposition. However,
modification of X-ray diffraction to the micro scale together with its application for very
heterogeneous real samples leads to deviations from the standard procedure .
Geological Applications:
XRD is the key tool in mineral exploration. Mineralogists have been among the
foremost in developing and promoting the new field of X -ray crystallography after
its discovery. Thus, the advent of XRD has literally revolutionized the geological
sciences to such a degree that they have become unthinkable without this tool.
Nowadays, any geological group actively involved in mineralogical studies would
be lost without XRD to unambiguously characterize individual crystal structures.
Each mineral type is defined by a characteristic crystal structure, whi ch will give a
unique X-ray diffraction pattern, allowing rapid identification of minerals present

within a rock or soil sample. The XRD data can be analyzed to determine the
proportion of the different minerals present.
The surface layer of soil, consisting of a mixture of mineral and organic matter,
reflects the nature and properties of the soil. Weathering of the minerals of the
earth’s crust originally derived most of the substances, including plant nutrients.
Among various substances, clay is an import ant soil constituent that controls its
properties and also influences its management and productivity. In addition to
commercial applications of clay minerals, they have great potential to fix pollutants
such as heavy metal organics and play an important r ole in cleansing the biosphere.
Despite the fact that excess clay induces unfavorable properties and requires more
energy for tillage operation, clay immensely improves soil fertility. Thus, it is
important to carry out quantitative and qualitative analysi s of clay minerals in soil.
X-ray diffraction has shown to be one of the best tool for the identification and
quantification of minerals present in soil (Shrivastava, 2009).
In another study the sand deposits from River Niger in Anambra State, southeastern
Nigeria, were characterized for their potential utilization as industrial raw materials
for ceramics and enamel wares. Physical, chemical, and mineralogical
characteristics of the sand sample were determined. XRD was used in the
mineralogical characterization. Results obtained were analyzed using the Bragg -
Wolf equation and International Centre for Diffraction Data software. The results
showed that the sample contained phyllosilicate minerals of the mica group and was
identified as shirozulite (KMn3 [Si3Al]O10[OH]2), a new manganese with dominant
monoclinic arrangement. The physicochemical analysis of the deposits confirmed
the XRD results. It was concluded that the samples could be utilized as industrial
raw materials for ceramics and enamel wares .
SOLVED PROBLEMS 03
58) The relationship between minimum wavelength of X -radiation generated from a target
metal and applied voltage is given by
(A) Bragg’s equation
(B) Moseley equation
(C) I11Kovik equation
(D) Duane-Hunt equation
59) Which of the following is not a target metal used in the Coolidge tube?
a) Rhodium
b) Cobalt
c) Gold
d) Silver
60) What are x-rays and what are their general applications?
X-rays constitute a small portion of the electromagn etic spectrum. These are high
energy radiations ranging from 0.01 to 10 nm wavelengths. These are capable of

penetrating most common solid materials and find use in nondestructive diagnosis. X -
rays are classified as hard x-rays with energies ranging from 5eV- 10keVandsoft x-rays
with energies in the range of 100eV to 50 keV. The most common application that
comes to mind is in medical diagnosis where x-rays are used to get images of broken or
cracked bones and foreign objects lodged inside the body. Besides medical diagnosis x-
rays find common use in destruction of cancerous cells, non-– destructive testing of
defects in mass produced materials, screening of passenger baggage for prohibited items
and studies on crystallinity and polymorphism in materials.
61) What are the disadvantages of the technique
The advantages far outweigh the disadvantages. However, some of the disadvantages are
that for identification purpose homogeneous and single phase materials are required for
identification. You have to purchase separately or create your own data base of
reference materials for confirmatory studies. The sample needs to be carefully prepared
as over grinding can introduce stress in the lattices.
01-04-04: APPLICATIONS TYPE II
d) Microelectronics Industry:
Since the microelectronics industry uses silicon and gallium arsenide single -
crystal substrates in integrated circuit production, there is a need to fully
characterize these materials using XRD. XRD topography can easily detect and
image the presence of defects within a crystal, making it a powerful
nondestructive evaluation tool for characterizing industrially important single -
crystal specimens.
The manufacture of ultra-large-scale integration technology can impose
significant strain within the constituent metallization because of the mismatch in
coefficients of thermal expansion between metallization and its surrounding
environment. The resulting stress distributions can be large enough to induce
voiding within Cu-based metallization, a key reliability issue that must b e
addressed. The interface between the Cu and overlying capping layers is a
critical location associated with void formation. By combining conventional and
glancing-incidence X-ray diffraction, depth dependent stress distributions that
develop in Cu films and patterned features were investigated. In situ annealing
and as-deposited measurements revealed that strain gradients were created in
capped Cu structures, where an increased in plane tensile stress was generated
near the Cu/cap interface. The interplay between plasticity in Cu and the
constraint imposed by capping layers dictates the extent of the observed
gradients. Cu films possessing caps deposited at temperatures where Cu
experienced only elastic deformation did not exhibit depth -dependent stress
distributions. However, all capped Cu samples exposed to temperatures that

induce plastic behavior developed greater tensile stress at the Cu/ cap interface
than in the bulk Cu film after cooling, representing a clear concern for the
mitigation of metallization voiding (Murray et al., 2012)
e) Glass Industry:
While glass is X-ray amorphous and does not itself give X -ray diffraction
patterns, there are still manifold uses of XRD in the glass industry. They include
identification of crystalline particles that ca use tiny faults in bulk glass and
measurements of crystalline coatings for texture, crystallite size, and
crystallinity.
The effects of high pressures on the structure of silica glass have been elucidated
using high-energy X-ray diffraction up to 43.5 GPa. A decrease in the first two
peak positions in the real-space pair-distribution functions up to 15 GPa
indicates initial shrinkage of the tetrahedral units. Above this threshold pressure
the Si-O bond peak shape becomes asymmetric and the average Si -O bond length
and coordination number both increase linearly with pressure. Also, strained
geometries in the
O
O correlations lead to a pronounced topological rearrangement of the second and

third nearest neighbors.
Nasu et al. Investigated the micro-mechanism of deformation behavior of
metallic glasses. The authors reported the results of direct observations of short -
range and medium-range structural change during tensile deformation of metallic
glasses by the high energy X-ray diffraction method. Cu50Zr50 and Ni30Zr70
metallic glass samples in a ribbon shape (1.5 mm width by 25 mm) were made
using the rapid quenching method. Tensile deformation added to the sample was
made by using special equipment adopted for measuring the high energy X -ray
diffraction. The peaks in pair distribution function g(r) for Cu50Zr50 and
Ni30Zr70 metallic glasses moved in a zigzag into the front and rear during
tensile deformation. These results of direct observation on atomic distribution
change for Cu50Zr50 and Ni30Zr70 metallic glass ribbons during tensile
deformation suggest that micro-relaxations occur.
f) Corrosion Analysis:
XRD is the only analytical method that readily provides information about the
phase composition of solid materials. The most important, versatile, and widely
used method for corrosion protection of steelwork is by paint or organic
coatings. Information on the microscopic level for a protective coating is

essential to understand the basic determinants of its attributes and improvement
requirements. Bitumen has been an important material for the protection of
steelwork in the world’s petroleum and other chemical and water industries.
Bitumen is, however, attended with some undesirable characteristics, and it can
vary widely in quality from one source to another. Results show that about 3.75
to 4.847% of each coating is constituted of 5 to 7 of 14 listed different mineral
phases, and there is variation in quantity and types of these phases even in
coatings produced at the same temperature with bitumen from the same source.
Corrosion ID can help to locate the origin of corrosion in a facility and, at the
same time, provide solutions to the problem. The formation of scale deposits
(e.g., corrosion deposits, formation materials, reaction products, catalysts, and
refractory materials) in sulfur recovery unit process equipment is one of the
major operational problems in the oil and gas industry. Thick deposits of various
types of mineral scale can grow within these units. Subsequently, these deposits
end up adversely affecting the production rate and quality. Zaidi et al. (2012)
conducted a study of 13 types of scale deposits that built up in different regions
of the equipment (converter, condenser, and vessel) using XRD, which is the best
available technique for the identification and quantification of all compounds
present in deposits. Additionally, the recent application of the Rietveld
refinement method in XRD quantitative phase analysis has produc ed great
advantages over conventional methods, such as the reference intensity ratio
method, in accuracy and convenience. The refinement results showed that while
iron oxide (magnetite and hematite) corrosion products were found in the steam
drum, several case studies show that sulfates (iron, sodium, and ammonium) are
the major deposit compounds built up in the condenser. A high weight percentage
of hematite indicated the presence of dissolved oxygen in the boiler feed water.
The deposits accumulated in the converter are titanium and aluminum oxide,
which indicates the leakage of a catalyst. Sulfur and carbon were also detected
from the line. The findings will help engineers to overcome the problems by
devising the right corrective procedures.
SOLVED PROBLEMS 04
62) Which of the following crystals are not suited for x -ray grating?
a) Topaz
b) Lithium fluoride
c) Calcium fluoride
d) Sodium fluoride
63) The x-rays generated come out of the Coolidge tube through which of the following?
a) Beryllium window
b) Tungsten window
c) Collimator
d) Target material

63) What are the common application areas of Powder XRD?
Powder XRD has proved to be a versatile tool for rapid and non -destructive testingof
materials and has found applications in several area s such as pharmaceuticals, foods,
geological samples and minerals, cosmetics, forensic investigation samples,
archaeological artifacts, polymeric films and corrosion product studies. The techniqueis
finding application in new fields with advancements in re search activities and industrial
materials.
64) What information is available from single crystal and Powder XRD techniques?
X-ray diffraction is broadly speaking divided into single crystal and powder diffraction
studies. Single crystal studies are carried out on a single homogeneous crystal with
optically clear faces. The size of the crystal selected should ideally be between 0.1 to
0.2mm across. The crystal is examined for uniformity with the help of a microscope
with polarising attachment before mounting on the goniometer head Single crystal
provides details on unit cells of crystals in terms of location of atoms, crystal systems,
bond angles and distances between atomic planes. The technique is non -destructive in
nature but takes a long time which may extend from several hours to days to complete a
single study.
CHECK POINT 01-04

1) When x-rays emitted from molybdenum are allowed to pass through a zirconium
filter, which of the following occurs?
2) Which of the following components are used to generate X -rays?
3) Using which of the following components is the generated x -rays focussed upon the
specimen?
4) In X-ray spectrometers, the specimen or the sample is plac ed after which of the
following components?
SUMMARY
X-ray diffraction (XRD) is an analytical technique used to characterize crystalline phases of
a wide variety of materials, typically for mineralogical analysis and identification of
unknown materials. Powder diffraction data are fundamentally derived by the atomic and
molecular arrangements explained by the physics of crystallography.
There are several advantages of XRD techniques in science laboratories:
 Nondestructive, fast, and easy sample preparation.
 High-accuracy for d-spacing calculations
 Can be done in situ
 Allows characterizing single crystal, poly, and amorphous materials
 Standards are available for thousands of material systems

KEY WORDS
X-raytube, sample holder, X-ray detector, Mono chromator, Collimator.
REFERENCES
Aaltonen, J.; Alleso, M.; Mirza, S.; Koradia, V.; Gordon, K. C.; Rantanen, J. Soli d Form
Screening—A Review. Eur. J. Pharm. Biopharm. 2009, 71, 23 –37. Andreeva, P.; Stoilov, V.;
Petrov, O. Application of X-ray Diffraction Analysis for Sedimentological Investigation of
Middle Devonian Dolomites from Northeastern Bulgaria. Geol. Balcanica 2011, 40, 31–38.
Benmore, C. J.; Soignard, E.; Amin S. A. Structural and Topological Changes in Silica
Glass at Pressure.Phys. Rev. B 2010, 81, Article ID 054105. Bish, D. L.; Post, J. E., eds.
Modern Powder Diffraction; Reviews in Mineralogy, vol. 20; Mi neralogical Society of
America: Chantilly, VA, 1989. Borghetti, G. S.; Carini, J. P.; Honorato, S. B.; Ayala, A. P.;
Moreira, J. C. F.; Bassani, V. L. Physicochemical Properties and Thermal Stability of
Quercetin Hydrates in the Solid State. Thermochim. Ac ta 2012, 539, 109–114. Brindley, G.
W.; Brown, G., eds. Crystal Structures of Clay Minerals and Their Identification.
Mineralogical Society: London, 1980. Cardell, C.; Guerra, I.; Romero -Pastor, J.; Cultrone,
G.; RodríguezNavarro, A. Innovative Analytical Methodology Combining Micro-X-ray
Diffraction, Scanning Electron Microscope-Based Mineral Maps, and Diffuse Reflectance
Infrared Fourier Transform Spectroscopy to Characterize Archeological Artifacts. Anal.
Chem. 2009, 81, 604–611.

1) IT ABSORBS RADIATION OF LONGER WAVELENGTH
2) Coolidge tube
3) COLLIMATOR
4) X-RAY TUBE
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=MW4PwJxxyt0
https://www.youtube.com/watch?v=VuxtifGWkvc
WIKIPEDIA
https://en.wikipedia.org/wiki/Ultraviolet%E2%80%93visible_spectroscopy
https://microbenotes.com/uv-spectroscopy-principle-instrumentation-applications/
OER
____
REFERENCE BOOKS
1. Steele, D., ‘Infrared Spectroscopy: Theory’, in Handbook of Vibrational
Spectroscopy, Vol. 1, Chalmers, J. M. and Griffiths, P. R. (Eds), Wiley, Chichester,
UK, 2002, pp. 44–70.

2. Barrow, G. M., Introduction to Molecular Spectroscopy, McGraw -Hill, New York,
1962.
3. Hollas, J. M., Modern Spectroscopy, 3rd Edn, Wiley, Chicheste r, UK, 1996
4. Fundamentals of molecular spectroscopy; C.N. Banwell, Tata McGraw Hill, New
Delhi.
5. Infrafed spectra of Inorganic and Coordination Compounds; K. Nakamoto; (John
Wiley & Sons, New York)
6. Molecular Spectroscopy, Principles and Chemical applications ; P,R singh & S.K.
Dikshit (S.Chand & Co. Ltd., New Delhi)

C REDIT 02

CREDIT 02-UNIT 01: THERMAL ANALYSIS
LEARNING OBJECTIVES
 Eexplain the principle of DTA, DSC and thermometric titration,
 Describe the experimental setup of DTA, DSC and thermometric titration,
 Interpret the analytical information from DTA and DSC curves and enthalpogram,
 Describe the applications of DTA, DSC and thermometric titration, and
 Distinguish between thermometric and classical titrimetry.
INTRODUCTION
 Thermal methods of analysis include a group of techniques in which change in

physical property of a material is measured as a function of temperature whil e the
substance is subjected to a controlled temperature programme.
 In modern era the new materials are studied with respect to – composition,
stability, chemical reactions and dynamic properties.
 Thermal methods are useful for these kind of analysis.
 These methods also provide information about the structure, composition, purity
and the temperature phase change of a material.
Now we will consider two similar thermal techniques, differential thermal analysis (DTA)
and differential scanning calorimetry, both these techniques have much wider applications
than TGA. In the last section of this unit, thermometric titrations and their applications
have been briefly discussed.
As defined earlier, in DTA, the heat changes within a material are monitored by measuring
the difference in temperature (∆T) between the sample and the inert reference. This
differential temperature is then plotted against temperature or time to get DTA curve (see
Fig. 11.1). In differential scanning calorimetry (DSC), the initial temperatures of the
sample and the reference are kept same. The amount of heat that has to be supplied to the
sample or reference to achive this equivalence in temperature is constantly measured over
the temperature range employed. This basically measures of the amoun t of energy absorbed
or evolved in a particular transition, and hence gives calorimetric measurements directly.
Similar to DTA Curve, DSC Curve can be obtained by plotting differential heat input to the

sample (expressed as a heating rate dH/dt) against te mperature and time (t) (see Fig. 11.2).
With this background, now we will consider the instrumentation and applications of DTA
technique.
02-01-01: PRINCIPAL OF THERMAL ANALYSIS
Definition of thermal analysis:
A group of techniques in which a property of the sample is monitored against time or
temperature while the temperature of the sample, in a specified atmosphere, is programmed.
This defines Thermal Analysis includes all the methods of measuring the sample properties
while the sample temperature is program-controlled.
Thermal Analysis instrument includes the followings:

 Detection Unit: Furnace, sample and reference holder, and sensor, heat and cool the sample in
the furnace, and detects the sample temperature and property.
 Temperature Control Unit: Controls the furnace temperature.
 Data Recording Unit: Records the signals of sensor and sample temperature, and analyzes
them.
Temperature control, data recording and analysis are all computer -controlled. The
combination of the furnace and sensor enables the various types of the measurement
techniques. This computer can be connected to the several instruments which has the
other types of measurement techniques, enables the simultaneous measurement and
analysis.
Table 1 shows the measurement techniques for each property. Each technique is called DTA,
DSC, TG, TMA and DMA.

* Thermocouple electromotive force.
Table 2 shows which effects and properties found in various materials are measured in each
technique.
The main application areas of DSC concern the determination of the melting, the glass
transition, the crystallization, the chemical reactions, the thermal history, and the specific
heat capacity. Though the sublimation, the evaporation, and the thermal decomposition can
also be measured, this technique is not usually used because of the mass change by the
decomposition and the corrosion of the sensor by the decomposed gas.
TG measures the mass changes by the evaporation, the dehydration, the decomposition, and
the oxidation reaction. By the simultaneous measurement by TG connected with DTA, the
exothermic and the endothermic phenomena can be measured from DTA.

TMA measures the phenomena caused by deformation including the thermal expansion, the
thermal shrinkage, the glass transition, and the curing re action. Though the melting and the
crystallization can measure, there is case of the adhesion of the sample to the probe by the
melting.
DMA measures the changes in the molecular motion and the molecular structures such as
the relaxation, the crystallization, and the curing reaction. It also measures the melting at
the early stage until the melt flow occurs.
Thermal Analysis instrument includes the followings:
 Detection Unit: Furnace, sample and reference
 Holder, and sensor, heat and cool the sample in the furnace, and detects the
sample temperature and property.
 Temperature Control Unit: Controls the furnace temperature.
 Data Recording Unit: Records the signals of sensor and sample temperature, and
analyzes them.
 Temperature control, data recording and anal ysis are all computer-controlled.
 The combination of the furnace and sensor enables the various types of the
measurement techniques.
 This computer can be connected to the several instruments which has the other
types of measurement techniques, enables the simultaneous measurement and
analysis.
Classification of thermal techniques:
SOLVED PROBLEMS 01
65) Which of the following option is appropriate for the TGA and DTA?

a) TGA and DTA measures only weight
b) TGA measures only weight while DTA measures other e ffects
c) TGA and DTA measures only temperature
d) TGA measures only temperature while DTA measures other effects
66) In the schematic DTA sequence having reversible and irreversible changes, starting
with the hydrated material, which of the following steps o ccurs first on heating?
a) Esterification
b) Methylation
c) Rehydration
d) Dehydration
SHORT ANSWER QUESTIONS 01
67) What is DSC?
a) DSC is a thermal analysis technique that measures heat flow as a function of time
and/or temperature. This correlates to how a material responds to changes in
temperature. The process involves applying heat or cold to see how it affects a
material’s heat capacity. These changes in heat capacity are measured as changes in
heat flow.
68) What are the Advantages of DSC?
1) DSC provides incredible ease and speed in tracking and analyzing material
transitions due to temperature changes. In particular, it’s a valuable tool for
tracking heat capacity, glass transitions, melting point and crystallinity.
69) What are the different types of thermal analysis?

70) Why is thermal analysis importent?
71) What are the two main techniques for the thermal analysis?
02-01-02 DIFFERENTIAL THERMAL ANALYSIS (DTA)
Differential thermal analysis is the most widely used and is probably a very suitable method
for the identification and estimation purposes especially in the case of soils (clays) and
minerals. The chemical or physical changes which are not accompanied by the change in
mass on heating are not indicated in thermo gravimetric but there is a possibility that such
changes may be indicated in DTA.
A) Principle:

Differential thermal analysis is a technique in which the temperature of the
substance under investigation is compared with the temperature of a thermally inert
material such as α-alumina and is recorded with furnace temperature as the
substance is heated or cooled at a predetermined uniform rate. The range of
temperature measurable in the course of DTA is much larger than TG determination.
Thus, during TG, pure fusion reactions, crystalline transition, glass transition and
crystallization and solid state reactions with no volatile product would not be
indicated because they provide no change in mass of the specimen. However, these
changes are indicated during DTA by endothermal or exothermal departure from the
base line. Since DTA is a dynamic method, it is essential that all aspects of the
technique be standardized in order to obtain reproducible results. These include
pretreatment of specimen, particle size and packing specimen, dilution of the
specimen and nature of the inert diluent. The principle of method consists in
measuring the change in temperature associated with physical or chemical changes
during the gradual heating of the substance. Thermal changes due to fusion,
crystalline structure inversions, boiling, dissociation or decomposition reactions,
oxidation and reduction reactions, destruction of crystalline lattice structure and
other chemical reactions are generally accompanied by an appreciable rise or fall in
temperature. Hence, all these are accounted in DTA. Generally speaking, phase
transitions, dehydration, reduction and some decomposition reactions produce
endothermic effects whereas crystallization, oxidation and some decomposition
reactions produce exothermic effects.
In DTA a sample of material under investigation (specimen) is placed by the side of
thermally inert material (the reference sample) usually calacite or α - alumina in
suitable sample holder or block. The temperature difference between the two is
continuously recorded as they are heated. The block is heated in an electric furnace
i.e. both are heated under identical conditions.
B) Characteristics of DTA Curves:
An idealized representation of the two major processes observable in DTA is
illustrated in Fig. 11.3, where ∆T is plotted on y-axis and T on x-axis. Endotherms
are plotted downwards and exotherms upwards. Similarly, the temperature of the
sample is greater for an exothermic reaction, than that of the reference, for
endotherms the sample temperature lags behind that of the refere nce.

When no reaction occurs in the sample material, the temperature of the sample remains
similar to that of reference substance. This is because both are being heated exactly under
identical condition i.e. temperature difference ∆T (Ts –Tr) will be zero for no reaction. But
as soon as reaction starts, the sample becomes either hot or cool depending upon whether
the reaction is exothermic or endothermic. A peak develops on the curve for the
temperature difference ∆T against temperature of furnace or time. Let us consider the DTA
curve in Fig. 11.3 again, where ∆T along the line AB is zero indicating no reaction but at B
where the curve begins to deviate from the base line corresponds to the onset temperature
at which the exothermic reaction starts and give rise to a peak BCD with a maximum at
point C. Where rate of heat evolution by the reaction is equal to the difference between the
rate of evolution of heat and inert reference material. The peak temperature C corresponds
to the maximum rate of heat of evolution. It does not represent the maximum rate of
reaction nor the completion of the exothermic process. Thus, the position of C does not
have much significance in DTA experiments.
At some determinant point the heat of evaluation process is completed and a fter this point
heat evaluation goes on decreasing up to D. The usefulness of the method arises from the
fact that peak temperature is normally characteristic of the material in the sample. Area of
the peak BCD is proportional to the amount of reacting mat erial. For endothermic reaction
the peak EFG will be obtained as shown in the idealised curve. This peak shows that the ∆T
i.e. (Ts–Tr) will be negative because heat is absorbed and conseque ntly Ts will be smaller
than Tr. Note the levels of base lines of extotherm curve, AB and DE. Both are at different
levels above x-axis. This is due to the fact that heat capacity of the sample has changed as a
result of the exothermic process. Similar explanation can be given for the difference in
levels of base lines of endotherm curve i.e. DE and GH. DTA curves are not only help in the
identification of materials but their peak areas provide quantitative informatio n regarding
mass of sample (m), heat of reactions (enthalpy change, ∆ H) and factors such as sample

geometry and thermal conductivity. If latter two factors are expressed by a factor K called
calibration factor, then peak area can be express as follows.
Peak area (A) = ± ∆ H m K …(11.1)
We will use +ve sign for endothermic reaction (∆H > 0) i.e. when the temperature of
the sample will lag behind the that of the reference, and negative sign for exothermic
reaction (∆H < 0) the temperature of the sample will exceed that of reference, factor K is
called calibration constant which is temperature dependent. It can be determined by
calibrating DTA with some standard. Once we know the value of K at a particular
temperature, the peak area can be used for quantitative analysis to determine the mass of
sample or energy (enthalpy changes) of a reaction. Beside this DTA curve also helps in
estimating heat capacity of a sample. As you can see in Fig. 11.3 that there is always a
difference in the base lines. The changes in heat capacity ( ∆ Cp) may be determined at a
particular temperature by measuring the difference in base lines i.e. displacement (d) since:
If area (A) is measured in cm2

−
and unit of ∆ H is J g–1, the unit of K will be cm2 J–1. 1 J 2 cm 1 g J g 2 cm = − K = In
DTA/DSC Cp is commonly expressed in mJ g –1 °C-1. Though in the SI units, it is
expressed as J mol-1K -1. An SI unit of change in enthalpy, ∆H, is kJ mol– 1. It is also
express as kcal mol–1 1 calorie = 4.2 J
C) Instrumentation:
In Fig. 11.4 is shown a block diagram of a differential thermal analyzer. It consists
of following basic components:
1. Furnace Assembly
2. Sample and reference holder with temperature detector
3. Temperature programmer
4. Temperature programmer
5. Atmosphere control equipment for furnace and sample holder
The instrument measures the differential temperature of the sample as a function of
temperature or time where the temperature rises at a constant linear rate.
Source of Uniform heating:
Nichrome (nickel and chromium alloy) furnace can be used up to 1300 °C, platinum and its
alloys up to 1750 °C and molybdenum (Mo) for higher range up to 2000 °C. A special type
of higher frequency induction heating may be used for higher temperatures.
Temperature regulating System:
Uniform rate of heating of the furnace is ensured through electronic temperature regulators.

Specimen Holder:
It is designed to accommodate even a small quantity of material and to give maximum
thermal effect. It can be of Pt, Ni, stainless steel, Ag and alloy such as Pt -Rh. Certain
ceramic materials such as sintered alumina , silica, fire clay, heat resistant glass and even
graphite have been recommended as material specimen holder for the sample under
investigation and reference material like (α-alumina).
Measurement of Temperature:
Rare metal alloy such as Pt- (Pt-10-13% Rh) are commonly used as thermocouple for
measuring the temperature. For higher temperature up to 2000 0C W-Mo thermocouple may
also be used. Very thin thermocouple is inserted in the sample and reference holder.
Temperature Recording System:
Visual galvanometric observations, though inconvenient can also be used when only a few
samples are to be investigated. Nowadays automatic pen and ink electronic r ecorder have
been found to be more convenient.
Direct recording of the heating curve:

When a sample is heated at a constant rate, the temperature function T, is linear up to the
moment when the sample undergoes change, its slope represents the rate of heating which
remains constant.
At the moment, when an exothermic or endothermic change takes place, the shape of curv e
changes as shown in . An exothermic reaction causes an increase in heating rate while
endothermic reaction causes a decrease in heating rate. The main disadvantage of this
method is its sensitivity, because small changes in the temperature causes small deviation in
linearity of the curve which some times are not observable. So, small temperature changes
occurring in the sample are generally not detected by this method. Since detector
thermocouples are opposed to each other, small difference between Ts and Tr can be
detected after suitable voltage amplification (Fig.11.4). Thus very small sample size may be
used in this method.
Thus recording of the differential curve is advantageous because it can record the small
change in enthalpy that is not accompanied by a change in weight.
D) Factors affecting DTA curves:
DTA is a dynamic temperature technique. Therefore, a large number of factors can
affect the resulting experimental curves. Similar to TGA curves, these factors can be
divided into the two groups: i) Sample factors, and ii) Instrumental factors The
Instrumental factors such as size and shape of sample holder, sample holder
material, heating rate of the sample, sensitivity of recording system, location of
thermocouple in the sample and atmosphere around sample. Most of these factors
are associated with instrumental design. We have very little control on these factors.
Sample characteristics includes amount of sample, particle size, packing density,
heat capacity and thermal conductivity, degree of crystallinity, dilutes of diluents,
swelling and shrinkage of the sample. In following lines we will concentrate on
some of the important factors in some detail.
6. Amount of Sample: In DTA analysis, peak area of DTA Curve is proportional to the
mass of the sample. Certainly this assumption is valid only over a certain range of amount
of the sample. Generally in DTA experiments, a few mg of powdered sol id sample is used.
7. Particle Size: In DTA experiments, Samples in the form of fine powers are generally
preferred except polymers, in which case we might have to use plastic fragments or
chopped fibers. When we are comparing between two materials, their sam ple should have
similar particle size.
8. Sample packing: Packing density of sample influences the shape of DTA Curve.
Tight packing influences the escape of volatiles and interaction of sample with atmosphere
of furnace due thermal experiments. Therefore, a reproducible method of packing the
sample is desirable.

9. Heating rate: It is observed that an increase in heating rate increases, the procedural
peak temperature, and some time it also increases peak area. Often high heating rate results
in poor resolution of fine peak in DTA curve. Therefore slower heating rate is preferred for
DTA experiments. Heating rate of 10° C min -1and 5° C min-1are commonly preferred.
10. Atmosphere around sample: Similar to DTG, a flowing gas is preferable to a static
atmosphere as in static atmosphere. There is a possibility of change of atmosphere around
sample on its degradation or decomposition especially in case of a volatile sample. In such
a case we generally use flowing gas technique. Flowing gas sweeps away volatile by
products and keeps homogenous atmosphere around sample. In Table 11.1, we have
summarized the major factor which can affect the DTA curve.
Rather empirical nature of the method gives rise to many difficulties originating from small
differences in technique e.g. the peak temperature normally used for reporting
differential thermal results as well as for identification is variable depending upon
the rate of heating, amount of active material, packing of specimen, type of
specimen holder etc. Thus standardization of technique is essential. In general, it is
essential that each apparatus should be calibrated from the mineral expected to be
the sample under investigation.
E) Sources of Errors:
There are a number of sources of errors in DTA, and they can lead to inaccuracie s in the
recorded temperature and weight data. Some errors may be eliminated by placing the
thermocouple at proper place and handing it with the care. For understanding we
discuss some common sources of errors during operation of a DTA.
i) Buoyance effect: If a thermally inert crucible is heated when empty there is usually
an apparent mass change as temperature increases. This is due to effect of change in
buoyancy of the gas in the sample environment with the temperature, the increase
convection and possible effect of heat from the furnace in the balance itself. Now, in
most modern instruments, this effect is negligible. However, if necessary, a blank

run with empty crucible can be performed over the appropriate temperature range
and calibrate the base line through mentioned procedure by individual instruments .
The resultant record can be used as a correction curve and results for subsequent
experiment performed in the same condition.
ii) Condensation on Temperature Sensor: Condensation of the sample will also
affect the sensitivity of a thermocouple for temperature measurement. This
can be avoided by maintaining a dynamic atmosphere around the sample in
the furnace so that all the condensable products may be driven by the
flowing gases.
iii) Fluctuation of thermostats.
iv) Reaction between sample and container
v) Convection effect from furnace
vi) Turbulence effect from gas flow
vii) Induction effect from furnace
It may noted that errors of type (iii) may be eliminated by properly placing balance in the
laboratory and maintaining constant power supply and error (v) can be avoided by sensible
choice of sample container. Last three types of errors (v -vii) have to be considered in the
design of the furnace, the balance and its suspension system. By avoiding excessive heating
rate and proper gas flow rate some of above mentioned errors may be eliminated. To further
minimize errors, DTA equipment should be calibrated both for temperature and peak area
determination with appropriate standards. For temperature substances like KNO3, In, Sn,
SiO2, BaCO3, etc. are used depending upon the temperature range used for the
experimental condition. For area calibration indium is often employed as a standard, but as
calibration factor K in case of DTA is temperature dependent, therefore, dependium upon
the temperature range of the experimental condition other standard are also used.
F) Interpretation of DTA Curve:
DTA curves of a pure compound represent characteristic of that compound for
physical chemical changes. Using DTA curve one can co -relate the changes in
energy because of thermophysical and chemical change occurring in a compound
because of heating the material. This can often provide us directly to the
temperature at which the physicochemical transition are occurring and which is
also used to identify the presence of respective elements or compounds qualitatively.
The change in DTA curve further gives information about the thermophysical
changes associated with mass change e.g. melting point, glass transition
temperature, crystallization temperature etc.
To further illustrate, let’s consider the example of CaC2O4.H2O for which DTA
curve is shown in Fig. 11.5. This curve indicates that out of three DTA peaks first is
endothermic in nature, second is exothermic and third one is again endothermic in

nature. The correlates the TGA results and confirms that the nature of reactions
occurring in the endothermic are because of desolvation and decarboxylation while
exothermic is due to decomposition followed by oxidation and finally formation of
stable oxide CaO with evolution of carbon dioxide gas. This can be explained by the
chemistry of decomposition of CaC 2 O 4 .H 2 O when it is heated.
DTA curves are useful both qualitatively and quantitatively. Similar to TGA, the
position and shapes of the peaks (curve) can be used to determine the composition
of the sample. As discussed earlier, Eq. 11.1 can be used to relate peak area with the
heat of the reaction and amount of sample used for analysis. But before using this
equation we should know the value of calibration constant, K, at the temperature
concerned. This can be achieved by the calibration of instruments with known
standards. However, the value of the calibration factor, K, may be eliminated from
the quantitative calibration by comparison of peak area of unkn own sample with the
known sample under identical condition. For example if A1 is the peak area of
known mass (m1) and A2 is the peak area of unknown sample having mass equal to
m2, then using Eq. 11.1 we can write.
Similarly, the heat of reaction of a unknown sample can also be calculated by

comparison with a sample of known heat of reaction. One thing keep in mind that

the calibration factor, K, in Eq. 11.1 is temperature dependent in DTA situation,
therefore both known and unknown sample should be run a t identical temperature.
You may have noticed in Fig 11.3 and 11.6 that the initial and final baselines of
peaks do not coincide. Therefore, determination of the area under the peak may be
subject to ambiguity. To resolve this problem a method for determin ation of the peak
area is illustrated in Fig. 11.6. Both baselines are extended to a perpendicular line
drawn from the maximum of the curve and the area under the two halves of the
curve are determined and added to give the total area.
The heat of reaction observed in DTA can be further used to calculate molar
enthalpy of reactions by using the formula:
∆Hm = ∆Hr × Mr / m … (11.3)
where, ∆Hm = molar enthalpy of reaction, ∆Hr = enthalpy of reaction, Mr = related
molar mass of the compound, m = Mass of substance used for analysis.
Determination of Heat Capacity:
The DTA curve is conveniently used to measure the heat capacity (specific heat). For
this purpose first a DTA curve is recorded for an empty container and then for the sample
placed in container is recorded in identical condition. The absolute change in temperature
(∆Tx) has been measured and put in the equation for calculations:
where Cp is the heat capcity at temperature T, T1 and T2 are diffenrential temperature

generated when the instrument is first run without any sample at all and then with the test
sample in position, H is the heating rate (dT/dt) and K is calibration factor. It can be
determined by calibration against standard substance of known enthalpy change.
Construction of Phase Diagram:
The Melting point can be recorded by DTA curve for a eutectic mixture of different sam ple
with variable composition. These melting points can be used to construct a phase diagram
The critical temperature of organic compounds can be determined by DTA if sealed sample

holder is used. The determination is used of cooling curve, a discontinuity is observed at
the critical temperature Tc. Curie point temperature making a sudden change at this point
can also be determined by this technique. The specific heat increases gradually upon the
curie point e.g 357 oC for nickel, observed simply by ploting dQ/dT or dT against
temperature.
Estimation of Transition temperature:
The precise determination of a transition temperature (e.g. M. P. and B.P.) up to a precision
of ± 0.3 oC over a wide range of heating rate. The temperature estimated for M.P. Tm or
B.P. TB, were most often selected from the portion peak as shown in Fig. 11.7. In this
figure first a base line meeting low and high temperature sides of the peak is drawn where A
is the intersection of extrapolated straight line portion of the low temperat ure side of the
peak with the base line. Further, point B is the inflection point of low temperature side of
the peak and point C is the extrapolated peak, while D is the extrapolated return to the base
line. Melting point Tm is measured by the using sampl e is closest to the temperature of
point C for sample and temperature at B for reference. In exceptional cases it may closer to
point D.
E) Applications:
Now we study in some more examples to understand how DTA is used in chemical
identification of a material (qualitative interpretation) comparing and for thermal stability
of materials. Such informations can be used to select material for certain end use
application, predict product performance and improve product quality.
Qualitative and Quantitative Identification of Minerals:
For the detection of any minerals in a sample, it is essential that it undergoes measurable
energy changes in the temperature range used. Since most of the minerals undergo such
changes, choice of an appropriate temperatur e range should have priority. However,
assuming a suitable range variation occurring in the minerals themselves may frequently
lead to difficulties in the interpretation of curves. Another complication arises from the fact

that certain minerals give reasonably characteristic thermal effect, sometimes clays do not
show similar result. Other difficulties may arise by the presence of organic matter.
Oxidation of organic materials if present masks the thermal effect of substance.
Consequently the analysis of such cases should preferentially be carried out in inert
atmosphere or in vacuum. Organic material some times be removable by a suitable solvent
or may be oxidized by treating with H2O2. When clays or ore contain organic material then
a broad exothermic peak appears between 200 – 600 0C. Thus the appearance of a broad
exothermic peak between 200-600 0C indicates the presence of organic material in a given
sample.
In practice however, difficulties do arise in a case where peak areas for two distinct
samples of same mineral give peaks at two different temperatures. It is, therefore, necessary
for qualitative work to know the peak area given by pure mineral identical to that in the
sample under investigation. This, however, is not possible. Another limitation in the
quantitative work in the occurrence of overlapping of peaks e.g. when Kaolinite and Illite
are present in the same sample almost completely overlapping takes place. A representative
DTA curve of some minerals are shown in Fig. 11.8. It may be observed that none of these
miners show an exothermic peak in the range 200 - 600 °C corresponding to organic
material as mentioned above.
Polymeric Materials:
DTA is a very useful technique for the characterization of polymeric materials in the light
of identification of thermophysical , thermochemical, thermo mechanical and thermo elastic
changes or transitions. It provides important parameters for polymer processing and its end

use. The DTA also provides useful information about quantitative aspect, degree of fusion,
crystallinity, phase equilibrium, heat of polymerization, degree of curing etc. A typical DTA
curve of a polymer is shown in Fig. 11.9 with labeled four transitions: glass transition,
crystallisation, melting and oxidation, abbreviated as Tg, Tc, Tm and Td respectively.
The DTA technique is also used for analyzing a polymeric mixture qualitatively and
quantitatively. The individual polymers exhibit their own characteristic peaks. The Fig. 11.9
is differential thermal curve of seven components pol ymeric mixture for their melting
points: Polytetrafloroethylene (PTFE), High Pressure (high dencity) Polypropylene (LPPE),
Low Density Polypropylene (LPPE), Polypropylene (PP), Polypropylene POM, Nylon 6,
Nylon 66.
It is shows characteristics peaks of all the polymers and hence confirm the presence of
individual polymers in the analyzed sample. The area under the peak is related to the heat
of reaction and related to the quantity of material present in the mixture. The DTA graph of
ethylene propylene block copolymer indicates two peaks for ethylene and propylene. On
comparing areas under the peaks it is found that 51 % ethylene and 49 % propylene present
in the analysed block copolymer. The peak height technique has been also employed to
measure the quantity of polysebacic anhydride in a epoxy resin - sebacic anhydride mixture.
Another important parameter determined from by DTA is glass transition (Tg), a second
order transition caused by relaxation of chain segment in the amorphous portion of a
polymer. The first evidence that a glass transition could be detected by DTA was provided

in (1957), where a transition at 28 °C was shown but not interpreted. As such this transition
is not associated with latent heat but rather a sudden change in specific heat to br ing a
liquid into the glassy state. The necessary condition is to cool it rapidly to approximately
two third of its melting point.
Tg/Tm =0.66
The glass transition of a polymer can be obtained using number average molecular mass M
ranging from 8 × 103 to 3 × 10 6 from expression:
Tg = [ ( 96.5 +/- 1.0 ) –( 2.8 +/- 0.1)] × 10 3 / M
The deduction about the slope of the glass transition as depicted by DTA curve:
a) The slope of the curve ∆T surface temperature should be sigmoidal.
b) The maximum value of ∆T at the glass transition temperature should be linearly
dependent on the heating rate.
c) The inflection point Tg should rise in temperature with the heating rate. It ha s been
shown that glass transition is associated with a sudden shift in base line.
The Tg depends on heating rate, volume fraction and molar mass. The DTA results
provide important information about polymerization reaction, mainly about heat of
polymerization, degree of curing, effect of catalysts, decomposition reaction and
radiation effects.
G) Measurement of Crystallinity:
A common application of DTA is the measurement of the mass fraction of crystalline
material in semi crystalline polymers. The method is based upon the measurement of the
polymer’s heat of fusion , ∆Hf, and the plausible assumption that this quantity is
proportional to the crystalline content . If by some process of extrapolation the heat of
fusion , ∆Hf*, of a hypothetical crystalline samp le is known then the mass fraction of a
crystallinity is
Thus, crystallinity of a polymer sample (X) can be determined by measuring the total
energy absorbed by the sample per gram ( ∆ H ) and subtracting the amount of energy
which would be absorbed by one gram of totally amorphous material [ (a) ∆ Hf ] in the
temperature interval, and then dividing by the heat of fusion of one gram of a perfectly
crystalline sample [ (c) ∆ Hf ], as expressed by following equation.
X = ∆H – ∆Hf (a)/ ∆Hf(c)
Another method for the determination of polymer crystallinity is based upon the ability of
the instrument to cool a molten sample rapidly and reproducibility to a selected
temperature where isothermal crystallization is allowed to occur. A number of

crystallization curves may be obtained at different temperatures. The difference in
crystallinity may be caused by branching, nucleation and molecular effect.
Degree of Polymerisation:
The area observed in DTA curve is directly related to heat of polymerization and can be
expressed in terms of per mole or per g. Consider the DTA graph of polymerization
process of trialkylcyanurate and triallylisocyanurate. Samples were prepared by mixing
two parts Al2O3 , one part monomer 0.1 part catalyst as a 50 % paste in tricresyl
phosphate and heating the mixture at a rate of 8 0C per minute. Typical values of heat of
polymerization as estimated from the peak area, are given in Table 11.1.
Further the area (size) of peak appears in DTA curve had a great value in assessing the
degree of curing. This is done by the residual cure remaining in a polymer system after
various treatments. This approach has been applied for estimation of degree of curing in an
unsaturated polyester-styrene copolymer cured at ambient temperature . The variation in
the size of the curve represents the percentage of curing in 2 hours 63 % , 3 hours 68.6 % 4
hours 74.3% , 5 hours 77.0 % and 6 hours 78.2%. Similarly the relative change in the heat
of reaction measured by DTA also gives information regarding role of cata lyst , degree of
crystallinity and decomposition of polymer samples.
Analysis of Biological Materials:
DTA has been widely used in the determination of thermal characteristics of bioorganic
molecules, the main constituent of body of living being. The bio m aterials are having
heterogenity as a significant feature. This describes it as multicomponent, molecular non
homogenous materials, in which component exist as continuous , separate and inter mixed
structures. Biological systems present complexity even in static state and then difficulty in
obtaining meaningful results and establishing correlation between thermal characteristics
and other physical chemical properties. However, the investigations carried out under
variable experimental condition indicate that DTA curve should be of value as ‘fingerprint’
of biological materials. The thermal characteristics of a number of biological materials
such as fresh biological materials and decomposed materials determined under different
atmospheric condition have been studied.
Fresh biological material consists of materials of active body of plants and animals. It is
always difficult to elucidate the chemical constituents of the plant materials. Information
obtained from the study of the simple molecules can not be nece ssarily applied directly to

heterogeneous system . In the study of such system indirect method has been applied e.g.
complete combustion, dilution effect, environmental effect etc. The DTA curves of four
leave samples of different plant in oxygen exhibit t wo pronounced exothermic effect in the
range 240-270 0C region. The first peak is invariably smaller than second one at least in
height always not in area apart from variation in peak temperature. The general similarity
in these curves may be inferred that leaves of the plants have at least same micro -chemical
composition.
The DTA curves for some plant materials have also been obtained in a static or air or
dynamic oxygen atmosphere, since it is difficult to distinguish between decomposition and
oxidation effects, which may overlap. Endothermic reaction such as dehydration or
volatilization while exothermic accompany combustion under inert atmosphere condition,
with oxidation reaction suppressed, such endothermic effect can be detected. Similarly the
analytical method is useful for analysis of high energy materials, explosives, ceramic,
cement and pharmaceuticals.
SOLVED PROBLEMS
72) On studying the reversible process during DTA which of the following is observed on
both heating and cooling?
a) Esterification
b) Hysteresis
c) Methylation
d) Carboxylation
73) Which one of the following options is not true for hysteresis?
a) It depends on the nature of the material
b) It depends on the structural change involved
c) It doesn’t depend on the experimental conditions
d) It doesn’t depend on the concentration of the electrode
74) Compound X has a relative molar mass of 98.4 K and heat of fusion ( ) ∆ H x of 6.85 kJ
mol–1. Compound Y has a relative molar mass of 64.3 and having same melting point as
X. 500 gm samples of each yield DTA peak areas of 60.0 cm2 and 45.0 cm3 for X and
Y, respectively. Calculate the heat of fusion of Y.
75) List the melting point of individual polymer samples from the DTA curve of Fig.
11.10.
76) What is Heat Capacity?
Heat capacity is a physical property of matter and is the amount of h eat necessary to
increase the temperature of a unit mass of a material by one degree. Heat capacity is an
extensive property, meaning that it scales with the overall size of the material. While

heat capacity is often treated as constant, it can fluctuate d epending on the system’s
temperature, pressure, and volume.
77) When Does Heat Capacity Matter?
Knowing a material’s heat capacity and enthalpy can help you determine the efficiency
of your processes. This information is beneficial if your company uses polym ers or
manufactures pharmaceuticals.
78) Write an expression, which relate the peak area with the amount of the sample. Give the
unit of calibration factor, Kr.
79) List the main factors which affect DTA curves
02-01-03: DSC
DIFFERENTIAL SCANNING CALORIMETRY (DSC):
In previous section we have studied DTA techniques in these methods, thermal reactions are
observed by measuring the deviation of the sample temperature from that of the reference
material. This deviation affects the DTA curve and decreases the sensitivity. There is
another technique called Differential Scanning Calorimetry (DSC) which have the
advantage of keeping the sample and reference at the same temperature and heat flow into
sample and reference is measured. This can be achieved by placing separ ate heating devices
in the sample and reference chambers. This is in contras to the DTA scheme, where both
sample and reference are heated by the same source.
1) Principle:
In DSC the heat flow is measure and plotted against temperature of furnace or time to get a
thermogram. This is the basis of Differential Scanning Calorimetry (DSC). The curve
obtained in DSC is between dH/dt in mJ s-1 or mcal s-1 as a function of time or
temperature. A typical DSC curve is shown in Fig. 11.11. The deviation observed above the
base (zero) line is called exothermic transition and below is called endothermic transition.
The area under the peak is directly proportional to the heat evolved or absorbed by the
reaction, and the height of the curve is directly proportional to the rate of reaction.
Therefore Eq. 11.1 is equally valid for DSC scheme also. The only difference is the
calibration factor K in case of DSC is independent of temperature. This is a major
advantage of DSC over DTA.

2) Instrumentation:
The block diagram of a DSC instrument as shown in Fig. 11.12a, essentially works on the
temperature control of two similar specimen holder assemblies. The left half of the block
diagram represents the circuit for differential temperature control while right hand side
indicates that for average temperature control. In the average temperature control circuit,
the temperature of the sample and reference are measured and averaged and the heat output
of the average heater is automatically adjusted so that the average temperature of the
sample and reference increases at a linear rate. The differential temperature use control
circuit monitors the difference in temperature between the sample and reference and
automatically adjust the power to either the reference or sample chambers to keep the
temperatures equal. For getting a thermogram, the temperature of the sample is put on the
x-axis and the difference in power supplied (in terms of J s -1 or cal. s–1) to the two
differential heaters is displayed on the y-axis.

Fig. 11.12 b illustrates the heating arrangement in sample and reference compartments.
Here the sample and reference compounds are provided with their own separate heaters, as
well as their own temperature sensors so that both S and R are maintained at identical
temperature by controlling electrically the rate at which heat is transferred to them.
In DSC, samples for analysis range in size from 1 to 100 mg are placed in a sealed sample
container. A wide range of heating rate (0.5 to 80°C/min) can be used, DSC instruments are
generally sensitive energy detect heat evolution or absorption at a rate less than one
millicalories per second. Electrical signals are amplified and recorded similar to TGA and
DTA.
During thermal process reactions either liberate or absorb heat. Thus, w hen ∆ H is
positive (endothermic reaction), the sample heating device is energized and a positive
signal is obtained; when ∆ H is negative the reference heating device is energized and a
negative signal is obtained. An idealized representation of the three major processes
observable in DSC is given in Fig. 11.13. The peak areas in DSC are proportional to the
amount of sample, the heat of reaction and similar to DTA peak area can be expressed by
following equation.
Peak area (A) = ± ∆ HmK … (11.6)

where ∆ H represents sample enthalpy change and m is the mass of sample and K is a
constant called calibration factor. Unlike DTA it is independent of temperature. Using
above Eq. 11.6, we can determine enthalpy change for a reaction directly from peak area,
if we known the value of K. We can also determine enthalpy change by comparing the ∆ H
of the sample with the known ∆ H of the standard. i.e.,
where ∆ Hs is the enthalpy change for sample, ∆ Hk is the enthalpy change for known
standard, ms and mk are masses of sample and known standard respectively, and As and Ak
represents the area of peaks of sample and standard materials, respectively.

DSC technique is not only sensitive for the determination of ∆ H, but it is also very
sensitive for the determination of heat capacities (Cp). when a sample is subjected to a
heating programme is DSC, the rate of heat flow into the sample is proportional to its heat
capacity. This may be detected by the displacement of the base line as illustrated in Fig.
11.13. The value of Cp may be determined at a particular temperature by measuring this
displacement (d). :
Using Eq. 11.9, we can deduce the unit of Cp. In DSC curve displacement (d) will be
measured in mJ s–1. If heating rate is in °C s–1- and m is expressed in g, then,
Cp can also be expressed in term of mcal. as 1 1 mCal g C − − [conversion factor for J and
Cal. is: 1 calorie = 4.2 J].
In practice we normally measure the base line shift by reference to a base line obtained for
empty sample and reference pans. To further minimize experimental error we usually
determine heat capacity of the sample by comparing with the known heat capacity of the
standard.
where, H 1 and H 2 are differential heat generated when the instruments is first run without
any sample at all and then with the test sample in position (in DSC curve (H2 – H1) is
expressed as displacement, d). K′ is calibration factor, it can be determined by calibration
against standard substance. However, K′ from the Eq. 11.10 can be eliminated, if a material
with a known heat capacity is used to calibrate the instrument.
Once of the commonly used standard is α -aluminium oxide (Al2O3) or synthesized
sapphire for which specific heat has been determined to five significant figures in the
temperature range 0 to 1200 K. After the base line and sample program, a third program is
run with a weighed sapphire structure. At any temperature T, following equation applies:

where d and d ′ are ordinate deflections (displacements) due to the sample and the standard
respectively, m CP ′ ′ are mass and heat capacity of the standard. Dividing the Eq. (11.11)
by (11.12) we get
Thus the calibration requires only the comparison of the two displacement values at the
same temperature . We can easily calculate value of Cp on putting the rest valu es in the Eq.
11.13. The basic components of DSC are quite similar except the differential energy
measuring system. In DSC, two principle works: one based on power compensation and
other heat flow method. In power compensation method smaller secondary heat er are
attached two equalizing the generated energy difference between sample and reference
materials. While in heat flow technique heat flux passing through sample and reference are
evaluated and their difference is related energy consumed or released in the thermal
reactions.
3 ) Factors Affecting DSC Curve:
In the beginning of this block we talked about the lowest temperature, Ti at which the onset
can be detected by the instrument operating under particular conditions. We may like to call
this as transition temperature, which is not correct. Actually in a DSC experiment, both Ti ,
Tf and Tc (the final temperature at which the decomposition is completed) do not have
fundamental significance, but they can still be a useful characteristic of a DSC curve. Th e
term procedural thermogram, often used for the temperature at which temperature change
appears to commence. This indicates that a start of thermal reaction, temperature does not
have a fixed value, but depends on the experimental procedure employed to ge t it. Similar
to this there are many factors which influence a DSC curve. These factors may be due to
instrumentation or nature of sample. We have listed the main factors which affect the shape,
precision and accuracy of the experimental results:
1. Instrumental factors:
a) Furnace heating rate.
b) Recording or chart speed
c) furnace atmosphere
d) Geometry of sample holder/ location of sensors
e) Sensitivity of recording mechanism.
f) Composition of sample container.
2. Sample Characteristics:
a) Amount of sample
b) Solubility of evolved gases in sample.
c) Particle size

d) Heat of reaction
e) Sample packing
f) Nature of sample
g) Thermal conductivity.
4) Sources of Error:
There are a number of sources of error in DSC, and they can lead to inaccuracies in the
recorded data of heat. Some of the errors may be corrected by placing the thermo balance at
proper place and handing it with the care. For understanding we are discussing some
common source of errors during operation or common as discussed in DTA except the in
accuracy caused by secondary heaters and thermostats.
Errors can be avoided by proper placing of instrument in the laboratory, maintaining
operating temperature, and constant power supply. By avoiding excessive heating rate and
proper gas flow rate other errors can be also avoided.
To further minimize the errors during experiments, similar to DTA, DSC instruments are
also be calibrated for the temperature and peak area measurements with suitable standards.
The only difference is that calibration constant in DTA situation is temperature dependen t
to a significant degree. Therefore in DTA measurement, we should calibrate peak areas
using a standard which provide a reference peak in a same temperature range as the test
sample. In DSC situation, K is independent of temperature. Therefore, it require s simple
steps for the calibration of the instrument. For peak area calibration we require standard of
high purity and accurately known enthalpy of fusion ( ∆ Hf ) are required. Few examples of
calibration standards are indium (In), benzoic acid, tin, lead , silver, gold, etc.
5) Interpretation of DSC Curve:
DSC curve of a pure compound is a fingerprint of that compound in the context of
transition temperature as well as heat required for that transition. Therefore, DSC curve can
be used to infer about the presence of a particular compounds and its thermal behaviour.
The peaks observed shifting of base line either up or down. A typical DSC curve is shown
in Fig 11.11. The peak above the base line is exothermic while down the base line is
endothermic.
We have seen above how area under DSC Curves is related to the amount of energy released
or absorbed in a physico-chemical change. It has been shown that under certain conditions
the area under the peak is proportional to the amount of heat evolved in a reactio n.
So this area under the curve is used for stochiometric ratio of analyzed compounds
(quantitative interpretation). Now we see in next example how it can be used to compare
thermal stability of a material for physical state and chemical states .This can b e used for
chemical identification of a material (qualitative interpretation). Such information can be
used to select material for certain end-use application, predict product performance and
improve product quality. DSC Curves of a polymeric mixture and p robable transitions are

shown in Fig. 11.14 for illustration about probable change in behaviour of a polymer
sample.
The DSC technique is more sensitive than DTA and it provides clear presence of a thermal
events occurring during course of heating of time ageing of material . Thus, the information
acquired by DSC is more realistic. The technique is used for the presence of polymorphism,
degree of crystallinity, curing fraction etc. Curves clearly indicate that Fig. 11.13is showing
the peaks for the glass transition, ordering, melting and decomposition of individual
polymers. The ratio of areasunder the curve by dividing the enthalpy of heat of
decomposition, provides the ratio of individual monomers in a analysed copolymer sample .
The heat of reaction (∆Hr) observed in DSC can be further used to calculate molar enthalpy
of reactions by using following formula:
∆Hm = ∆Hr × Mr /m
Where, (∆Hm = molar enthalpy of reaction , ∆Mr = relative molar mass of analysed
compound, m = Mass of substance used for analysis .
6) Applications:
Differential scanning Calorimetry (DSC) used to measure energy changes as a function of
temperature or time. A typical graph is shown in Fig. 11.13. Using this technique it is
possible to observe a number of characteristic properties of a sample like fusion,
crystallization, glass transition temperatures (Tg) as well as other thermo chemical
reactions. DSC can also be used to study oxidation, as well as other chemical reactions.
Glass transitions may occur as the temperature of an amorphous solid is increased. These
transitions appear as a step in the baseline of the recorded DSC signal. This is due to the
sample undergoing a change in heat capacity; no formal phase change occurs. As the
temperature increases, an amorphous solid will become less viscous. At some point the
molecules may obtain enough freedom of motion to spontaneously arrange themselves into
a crystalline form. This is known as the crystallization temperature (Tc). This transition
from amorphous solid to crystalline solid is an exothermic process and results in a peak in
the DSC signal. As the temperature increases the sample eventually reaches its melting
temperature (Tm). The melting process results in an endothermic peak in the DSC curve.

The ability to determine transition temperatures and enthalpies makes DSC an invaluable
tool in producing phase diagrams for various chemical systems. The technique is widely
used across a range of applications, both as a routine quality test and as a research tool. The
equipment is easy to calibrate, using low melting indium for example, and is a rapid and
reliable method of thermal analysis. The few notable specific applications of DSC are:
The result of a DSC experiment is a curve of heat flux versus temperature or time. There
are two different conventions: exothermic reactions in the sample shown with a positive or
negative peak. This curve can be used to calculate enthalpies of transitions. This is done by
integrating the peak corresponding to a given transition. It can be shown that the enthalpy
of transition can be expressed using the following equation:
∆H = KA
where ∆H is the enthalpy of transition, K is the calorimetric constant, and A is the area
under the curve. The calorimetric constant will vary with the instrument and can be
determined by analyzing a well-characterized sample with known enthalpies of transition.
Most of well known spectroscopic methods of great value in the qualitative and quantitative
chemical analysis are based on our ability to measure energy absorption or emission caused
by transition from one energy state to another. The great potential of thermal spectroscopy
for quantitative analysis was not realized in the past because of the absence of a suitable,
fast scanning, the calibration run for the synthetic compounds and the base line technique
used in the area measurement and can be used for the quantitative analysis of constituents
present in the fiber blend.
Many materials can exist in two or more different crystal line forms. The chemical
reactivity and physical properties of different forms vary frequently one to another.
Technological handling requires one of the perfect suitable form, hence the phenomenon is
of great importance in chemistry and conveniently studied by DSC.
DSC may also be used in the study of liquid crystals. As matter transitions between solid
and liquid it often goes through a third state, which displays properties of both phases. This
anisotropic liquid is known as a liquid crystalline or mesomorphous state. Using DSC, it is
possible to observe the small energy changes that occur as matter transitions from a solid to
a liquid crystal and from a liquid crystal to an isotropic liquid.
DSC curves may also be used to evaluate puriting of a drug and polymer. This is possible
because the temperature range over which a mixture of compounds melts is dependent on
their relative amounts. This effect is due to a phenomenon known as freezing point
depression, which occurs when a foreign solute is added to a solution. (Freezing point
depression is what allows salt to de-ice sidewalks and antifreeze to keep your car running in
the winter.) Consequently, less pure compounds exhibit a broadened melting peak that
begins at lower temperature than a pure compound. DSC is used widely for examining
polymers to check their purity and composition. Melting point and glass transition

temperature for most polymers are available from standard compilations, and the method
can show up possible polymer degradation by the lowering of the expected melting point,
Tm. It depends on the molar mass of the polymer, so lower grades will have lower me lting
points than expected.
In pharmaceutical industry it is necessary to have well -characterized drug compounds in
order to define processing parameters. For instance, if it is necessary to deliver a drug in
the amorphous form, it is desirable to process the drug at temperatures below those at
which crystallization can occur. The above mentioned transition are well observed in DSC
curve and used in industry regularly
There are two important criteria for characterization of waxes and fats by DSC:
1) Although melting peak shape of wax and wax formulations can be quite complex ,
they are much less sensitive than fats to variation in the crystallization condition.
2) The crystallization of waxes is easily nucleated with the result that solidification
occurs readily with little or no super cooling. In fact the crystallization peak for
most waxes is virtually mirror image to its melting point. Although reading of DSC
thermogram and applying to these criterions, we can easily make statement whether
the supplied material is wax or fat.
Using differential scanning calorimetry to study the oxidative stability of samples generally
requires an airtight sample chamber. Usually, such tests are done isothermally (at constant
temperature) by changing the sample atmosphere. First, the sample is brought to the desired
test temperature under an inert atmosphere, usually nitrogen or organ. Then, oxygen is
added to the system. Any oxidation that occurs is observed as a deviation in the baseline.
Such analysis can be used to determine the stability and optimum storage conditions of a
compound
A more specific application of DSC where DTA cannot be employed is the detection of
magnetic transition in the materials. The magnetic transition are of second order with ∆H=0
but with the a maximum heat capacity at the transition temperature. Technique is sensitive
to detect these minor variations. A typical DSC curve for a magnetic transition is shown in
Fig. 11.15. Similarly glass transition can be detected easily with DSC.
7) Advantages of DSC:

1. Small sample size 1 to 10 mg.
2. Simple and rapid procedure of analysis, typically 15 to 30 min. per determination.
3. Ideal for comparison of sample purity for example in quality control.
4 Does not require high absolute temperature accuracy ( in contrast with melting point
depression method.
5 Does not require calibration with known impurity levels, cryoscopic constant is
obtained simultaneously.
6 The use of melting rather than a freezing curve avo id problems associated with
super cooling of sample , poor crystallizability from melt , instability in the melt etc.
SOLVED PROBLEMS
3) In the application of DTA and DSC which of the following parameters is measured
for the glasses?
a) Concentration of the glass
b) Solubility of the glass
c) Cooling temperature
d) Transition temperature
4) DTA can be used for which of the following process?
a) Line positions of the crystals
b) Mechanical properties of the crystals
c) Phase diagrams
d) Catalytic properties of enzymes

5) What is Glass Transition?
A glass transition is what happens when a noncrystalline solid or amorphous material
melts. Amorphous solids have no organization — this is the reason for their transparency.
When you apply heat to an amorphous solid, its heat capacity increases. When the material
accumulates enough energy, it experiences a glass transition in which it becomes hard, rigid
and brittle. The glass transition is a reversible transition, like melting.
6) When Does Glass Transition Matter?
The glass transition temperature is an excellent indication of a material’s composition and
can identify potential performance issues — especially when using synthetic high polymers
for manufacturing or storage. That’s because additive s can change glass transition
temperature. Also, a material’s properties can affect the degree of polymerization, stiffness
and flow. Glass transition temperatures are often used to determine optimal storage
conditions in pharmaceutical and food products.
7) Write the essential differences between a DTA and DSC.
8) DTA and DSC, which method you will prefer for quantitative purposes and why?

02-01-04: THERMO GRAVIMETRIC ANALYSIS
1) INTRODUCTION: Thermo gravimetric analysis (TGA) is the most widely used
thermal method. It is based on the measurement of mass loss of material as a function of
temperature. In thermogravimetry a continuous graph of mass change against temperature is
obtained when a substance is heated at a uniform rate or kept at constant temperature. A
plot of mass change versus temperature (T) is referred to as the thermogravimetric curve
(TG curve). For the TG curve, we generally plot mass (m) decreasing downwards on the y
axis (ordinate), and temperature (T) increasing to the right on t he x axis (abscissa) as
illustrated in Fig. 10.1. Sometime we may plot time (t) in place of T. TG curve helps in
revealing the extent of purity of analytical samples and in determining the mode of their
transformations within specified range of temperature .
In thermogravimetry, the term ‘decomposition temperature’ is a complete misnomer. In a
TG curve of a single stage decomposition, there are two characteristic temperatures; the
initial Ti and the final temperature Tf (see Fig. 10.1). Ti is defined as the lowest
temperature at which the onset of a mass change can be detected by thermo balance
operating under particular conditions and Tf as the final temperature at which the particular
decomposition appear to be complete. Although Ti has no fundamental signi ficance, it can
still be a useful characteristic of a TG curve and the term procedural decomposition
temperature has been suggested. The difference Tf – Ti is termed as reaction interval. In a
dynamic thermogravimetry a sample is subjected to continuous in crease in temperature
usually linear with time whereas in isothermal or static thermogravimetry the sample is
maintained at a constant temperature for a period of time during which any change in mass
is noted. Now we will take up the
Instrumentation commonly used to obtain TG Curve.
2) INSTRUMENTATION:
The instrument used in thermogravimetry (TG) is called a thermobalance. It consists of
several basic components in order to provide the flexibility necessary for the production of
useful analytical data in the form of TGA Curve as shown in Fig. 10.4.

Basic components of a typical thermobalance are listed below: i) Balance ii) Furnace:
heating device iii) Unit for temperature measurement and control (Programmer) iv)
Recorder: automatic recording unit for the mass and temperature changes These
components may be represented by simple block diagram as in Fig. 10.2
A) Balance: The basic requirement of an automatic recording balance are includes accuracy,
sensitivity, reproducibility, and capacity. Recording balanc es are of two types, null point
and deflection type. The null type balance, which is more widely used, incorporates a
sensing element which detects a deviation of the balance beam from its null position, A
sensor detects the deviation and triggers the restoring force to bring the balance beam to
back to the null position. The restoring force is directly proportional to the mass change.
Deflection balance of the beam type involve the conversion of the balance beam
deflection about the fulcrum into a suitable mass – change trace by (a) photographic
recoding i.e change in path of a reflected beam of light available of photographic
recording, (b) recording electrical signals generated by an appropriate displacement
measurement transducer, and (c) using an electr ochemical device. The different balances
used in TG instruments are having measuring range from 0.0001 mg to 1 g depending on
sample containers used.
B) Furnace : The furnace and control system must be designed to produce linear heating at
over the whole working temperature range of the furnace and provision must be made to
maintain any fixed temperature. A wide temperature range generally -150 °C to 2000 °C
of furnaces is used in different instruments manufacturers depending on the models. The
range of furnace basically depends on the types of heating elements are used.
C) Temperature Measurement and Control :Temperature measurement are commonly done
using thermocouples , chromal – alumel thermocouple are often used for temperature up
to 1100 °C whereas Pt/(Pt–10% Rh) is employed for temperature up to 1750 °C.
Temperature may be controlled or varied using a program controller with two
thermocouple arrangement, the signal from one actuates the control system whilst the
second thermocouple is used to record the temp erature.

D) Recorder:Graphic recorders are preferred to meter type recorders. X -Y recorders are
commonly used as they plot weight directly against temperature. The present instrument
facilitate microprocessor controlled operation and digital data acquisition and
processing using personal computer with different types recorder and plotter for better
presentation of data.
In Fig. 10.3, we have shown a schematic diagram of the specific balance and furnace
assembly as a whole to better understand the working of a thermobalance. In this diagram
you can clearly see that the whole of the balance system is housed in a glass to protect it
from dust and provide inert atmosphere. There is a control mechanism to regulate the flow
of inert gas to provide inert atmosphere and water to cool the furnace. The temperature
sensor of furnace is linked to the programme to control heating rates, etc. The balance
output and thermocouple signal may be fed to recorder to record the TG Curve.
E) Thermogravimatic Curves: So far we have discussed the instauration of TG now we turn

our attention to quantitative aspects of TG. As discussed earlier TG curves represent the
variation in the mass (m) of the sample with the temperature (T) or time (t). Normally, we
plot mass loss downward on the ordinate (y) axis and mass gain upwards as shown in Fig.
10.4.

Sometime we also record derivative thermogravimetric (DTG) Curves. A DTG curve
presents the rate of mass change (dm/dt) as a function of temperature, or time (t) against T
on the abscissa (x axis) as shown in Fig. 10.4 when substance is heated at uniform rate. In
this figure, the derivative of the Curve is shown by dotted lines.
3) SOURCES OF ERRORS IN TGA: There are a number of sources of error in TGA, and
they can lead to inaccuracies in the recorded temperature and mass data. Some of the errors
may be corrected by placing the thermobalance at proper place and handling it with great
care. For understanding we are discussing some common source of errors during operation
of a thermobalance.
i) Buoyance effect: If a thermally inert crucible is heated when empty there is usually an
apparent weight change as temperature increases. This is due to effect of change in
buoyancy of the gas in the sample environment with the temperature, the increase
convection and possible effect of heat from the furnace in the balance itself. Now, in most
modern thermobalances, this effect is negligible. However, if necessary, a blank run with
empty crucible can be performed over the appropriate temperature range. Th e resultant
record can be used as a correction curve for subsequent experiment performed in the same
condition. ii) Condensation on balance suspension: Condensation of the sample will also
affect the mass of the sample and consequently the shape of TG curv e .This can be avoided
by maintaining a dynamic atmosphere around the sample in the furnace so that all the
condensable product may be driven by the flowing gases.iii) Random fluctuation of balance
mechanism iv) Reaction between sample and container v) Con vection effect from furnace
vi) Turbulence effect from gas flow vii) Induction effect from furnace.
4) INTERPRETATION OF TG CURVES: TG curves of a pure compound are characteristic
of that compound. Using TG curve we can relate the mass changes to the stoic hiometry

involved. This can often lead us directly to the quantitative analysis of samples whose
quantitative composition is known. To further illustrate, let’s consider the example of TGA
curve of CaCO3, (Fig. 10.5.) This curve indicates that CaCO3 decomp oses in a single step
between 800° C and 950° C to form stable oxide CaO and the gas carbon dioxide. This can
be explained the chemistry of CaCO3 when it is heated
Now again consider the Fig. 10.5 (c), it indicates the % mass lost by the sample is 44
(100.1–56.1) between 800 and 950° C. This exactly corresponds to the mass changes
calculations based on stoichiometry of the decomposition of CaCO3 expressed by the
chemical Eq. (10.1). As in this case, percentage weight loss of CaCO3 will be
We have seen above how TG Curves is related to stoichiometry (quantitative

interpretation). Now we see in next example how it can be used to compare thermal
stability of materials (qualitative interpretation). Such information can be used to select
material for certain end-use application, predict product performance and improve product
quality. Fig. 10.6 gives TG Curves of some polymers. TG Curves clearly indicate that
polymer (PVC) is the least thermally stable and polymer (PS) is most thermally stable.
Polymer (PS) looses no weight at all below about 500o C and then decomposes abruptly by
about 600 o C. The other three polymers have all decomposed by about 450 o C. Polymers

(PMMA) decomposes more slowly overall than the others as indicated by slopes of TG
curves. TG curve of polymer (PMMA) has less slope than the others.
5) FACTORS AFFECTING TG CURVE:In the beginning of this units we talked about the
lowest temperature, Ti at which the onset of a mass change can be detected by the
thermobalance operating under particular conditions and Tf is the final temperature at
which the decomposition completed. We may like to call this as decomposition temperature,
which is not correct. Actually in TGA experiments, both Ti and Tf do not have fundamental
significance, but they can still be a useful characteristic of a TG curve and the termed
procedural decomposition temperature. It is often used for the temperature at which mass
change appears to commence. This indicates us that procedural decomposition temperature
does not have a fixed value, but depends on the experimental procedure employed to get it.
Similar to this there are many factors which influence a TGA curve. These factors may be
due to instrumentation or nature of sample. We have listed the main factors which affe cts
the shape, precision and accuracy of the experimental results in thermogravimetry.
1. Instrumental factors: i) Furnace heating rate. ii) Recording or chart speed iii) Furnace
atmosphere iv) Geometry of Sample holder/ location of sensors v) Sensitivity of
recording mechanism. vi) Composition of sample container.
2. Sample Characteristics: a) Amount of sample b) Solubility of evolved gases in sample.
c) Particle size d) Heat of reaction e) Sample packing f) Nature of sample g) Thermal
conductivity. Now we will take up some important factors in some detail.
6) APPLICATIONS OF TERMOGRAVIMETRIC ANALYSIS:In the previous section we
have seen how TGA can be used to understand the chemistry of decomposition of a
particular compound. TGA also provides information about the temperature range over
which a particular sample appears to be stable or unstable. We have also interpreted TG
curves qualitatively. Beside these there are many other applications of thermogravimetric
analysis. Some are listed below:

i) Purity and thermal stability. ii) Solid state reactions. iii) Decomposition of inorganic and
organic compounds. iv) Determining composition of the mixture. v) Corrosion of metals in
various atmosphere. vi) Pyrolysis of coal, petroleum and wood. vii) Roasting and
calcinations of minerals. viii) Reaction kinetics studies. ix) Evaluation of gravimetric
precipitates. x) Oxidative and reductive stability. xi) Determining moisture, volatile and ash
contents. xii) Desolvation, sublimation, vaporizations, sorption, desorption, c hemisorptions.
It is not possible to discuss all these applications at this level; it is worth to describe some
of the applications which are more common.
SOLVED PROBLEMS
9) For the decomposition of the anhydrous calcium oxalate, which of the following
steps occur?
a) Intermediates, transition state, product
b) Intermediates, anhydrous oxalate, calcium oxysalts
c) Intermediates, aqueous hydrates, calcium hydroxides
d) Intermediates, anhydrous calcium oxalate, calcium carbonate
10) Which of the following parameters can be used, using the DSC and DTA cells?
a) Catalytic properties of enzyme
b) Elasticity of crystals
c) Enthalpy of substances
d) Line positions of phases
11) Calculate the percentage mass change (m %) for the following reactions. i) Ca(OH)
)s( CaO )s( H
4∆
12) A mixture of CaO and CaCO3 is analysed by TGA. The result indicates that mass of
the sample decreases from 250.6 mg to 190.8 mg only between 600°C and 900°C.
Calculate the percentage of calcium carbonate in the mixture.

13) When Does Melting Point Matter?
Understanding a polymer’s melting point can help identify the impact that heat,
impurities and fillers have on product performance. Armed with this knowledge, you
can alter processes and product composition to ensure the product performs as expected
within normal temperature ranges.
14) What is the Melting Point?
The melting point is the temperature at which a material changes and goes from solid to
liquid. This state change happens because polymer chains fall out of their organized
structure, resulting in a disordered liquid.

15) List the different components of a thermobalance.
16) What are common source of errors in thermogravimetric analysis?
CHECK POINT 02-01

1) A rapid tga method is used for which of the following process?
2) Thermomechanical analysis (TMA) having mode of operation ----------
3) In thermomechanical analysis (TMA) tension mode is -----------
4) In DTA method, the sample temperature was recorded on ------------
SUMMARY
Thermo gravimetric Analysis (TGA) technique has been described for its basic principle,
instrumentation and applications. The interpretation of results and applications are
discussed by taking different examples. The elementary calculation are inclu ded to
elaborate the topics. The probable cause of errors, their remedies, interpretation of result
are also discussed.
KEY WORDS
Inelastic scattering,Hard Segment, Survey spectrum,High resolution Sectrum
REFERENCES
D.Q.M. Craig; “Dielectric Analysis of Pharmaceutical Systems”, Taylor and Francis,
London,1995
J. Goodwin and R. W. Hughes; “Rheology for Chemists: An Introduction”, Royal Society of
Chemistry, Cambridge, 2000
J. D. Ferry, "Viscoelastic Properties of Polymers," 3rd. edn., Wiley, New York, 198 0
N. G. McCrum, B. E. Read and G. Williams, “Anelastic and Dielectric Effects in Polymeric
Solids”, Dover, New York, 1991

1) Decomposition of reactions isothermally
2) 2
3) films and fibers
4) cooling
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=paaQfIaw7a8
https://www.youtube.com/watch?v=drLvk9p7fgg

WIKIPEDIA
https://www.sciencedirect.com/topics/materials -science/thermal-analysis
https://en.wikipedia.org/wiki/Thermogravimetric_analysis
OER
____
BOOKS
1. H.H.Willard , L.L.Merrit Jr., J.A. Dean , F.A.Settle Jr., Instrumental Method of Analysis,
Wadsworth Publishing Company , USA, 1986.
2. M.E. Brown, Introduction to Thermal Analysis, Kluwer Academic Publisher , London,
2001.
3. C.Duval, Inorganic Thermogravimetric Analysis, Elsevier Amsterdam, 1962.
4. P.D.Garn, Thermoanalytical Methods of Investigations, Academic Press, New York ,
1965.
5. W.W. Wandlandt , Thermal Analysis, Wiley , New York , 1986.
6. A.Blazek, Thermal Analysis, Van Nostrand Reinhold , London ,1972 .
7. H.Gunzzler and A.Williams , Hand Book of Analytical Techniques, Wiley – VCH ,
Weinheim , Vol -2, 2001. 8. G.W.Ewing , Analytical Instrumentation Handbook, Marcel
Dekker Inc, New York, 1990.

CREDIT 02-UNIT 02: THERMO MECHANICAL ANALYSIS
LEARNING OBJECTIVES
 To describe concept various thermal techniques for identification of stability of
chemical compounds
 Evaluate and quantify errors associated with measurements made using instrumental
techniques
 Thermal methods in qualitative and quantitative analysis and in materials science.
Thermal methods in qualitative and quantitative analysis and in materials science.
Thermal methods in qualitative and quantitative analysi s and in materials science.
 Obtaining basic knowledge on thermo analytical methods.
 Application of thermo analytical instruments in practice.
INTRODUCTION
The dimensional and mechanical stability of materials is of paramount importance to their

use in the everyday world where they may encounter a wide variation in temperature
through design or by accident. Many polymers are processed at elevated temperatures so as
to enable them to flow and be more amenable to fabrication. Food items are cooked,
pasteurised or otherwise heated or frozen. Ceramics are fired so as to consolidate their final
structure. The relationship between a material's dimensional and mechanical properties and
its temperature is studied by the techniques described within this chapter and, due to
common concepts, the effect of heat on the electrical properties of materials is also
considered.
02-02-01: THERMO MECHANICAL ANALYSIS

Thermomechanical Analysis (TMA) can be defined as the measurement of a specimen’s
dimensions (length or volume) as a function of temperature whilst it is subjected to a
constant mechanical stress. In this way thermal expansion coefficients can be determined
and changes in this property with temperature (and/or time) monitored. Many materials will
deform under the applied stress at a particular temperature which is often connected with
the material melting or undergoing a glass-rubber transition. Alternatively, the specimen

may possess residual stresses which have been “frozen -in” during preparation. On heating,
dimensional changes will occur as a consequence of the relaxation of these stresses.
Stress (σ) is defined as the ratio of the mechanical force applied (F) divided by the area
over which it acts (A):
σ = F/A (1)
The stress is usually applied in compression or tension, but may also be applied in shear,
torsion, or some other bending mode as shown in Figure 1. The units of stress are N m -2 or
Pa.
If the applied stress is negligible then the technique becomes that of thermodilatometry.
This technique is used to determine the coefficient of thermal expansion of t he specimen
from the relationship:
α.l0 = dl/dT (2)
where α is the coefficient of thermal expansion (ppm °C -1 or µm m-1 °C-1), l0 is the

original sample length (m) and dl/dT is the rate of change of sample length with
temperature (µm °C-1).
INSTRUMENTATION:

A schematic diagram of a typical instrument is shown in Figure 5. The sample is placed in a
temperature controlled environment with a thermocouple or other temperature sensing
device, such as a platinum resistance thermometer, placed in close proximity. The facility to
circulate a cryogenic coolant such as cold nitrogen gas from a Dewar vessel of liquid
nitrogen is useful for subambient measurements. The atmosphere around the sample is
usually controlled by purging the oven with air or nitrogen from a cylinder. Because o f the
much larger thermal mass of the sample and oven compared to a differential scanning
calorimeter or a thermobalance, the heating and cooling rates employed are usually much
slower for TMA. A rate of 5°C min-1 is usually the maximum recommended value f or good
temperature equilibration across the specimen. Even this rate can be a problem for some
specimens where appreciable temperature gradients can exist between the middle and ends
of the sample particularly around the test fixtures - which can represent a significant heat
sink.
For compression measurements (as illustrated) a flat -ended probe is rested on the top
surface of the sample and a static force is applied by means of a weight or (more commonly
in the case of modern instrumentation) an electromagnetic motor similar in principle to the
coil of a loudspeaker. Some form of proximity sensor measures the movement of the probe.
This is usually achieved by using a linear variable differential transformer (LVDT) which

consists of two coils of wire which form an electrical transformer when fed by an AC
current. The core of the transformer is attached to the probe assembly and the coupling
between the windings of the transformer is dependent upon the displacement of the probe.
Other transducers such as capacitance sensors (which depend on the proximity of two plates
– one fixed the other moving) or optical encoders are used in certain instruments.
Most commercial instruments are supplied with a variety of probes for different
applications (Figure 6). A probe with a flat contact area is commonly used for thermal
expansion measurements where it is important to distribute the applied load over a wide
area. Probes with sharp points or round-ended probes are employed for penetration
measurements so as to determine the sample’s softening temperature. Films and fibres,
which are not self-supporting, can be measured in extension by clamping their free ends
between two grips and applying sufficient tension to the specimen to prevent the sample
buckling. Volumetric expansion can be determined using a piston and cylinder arrangement
with the sample surrounded by an inert packing material such as alumina powder or silicone
oil.
The equipment must be calibrated before use. The manufacturers, as well as various
standardisation agencies, usually provide recommended procedures. A full list of standard
methods and calibration protocols for all thermal methods is given in the Appendix.
Temperature calibration is usually carried out by preparing a sample comprising a number
of metal melting point standards, such as those used for differential scanning calorimetry,
sandwiched between steel or ceramic discs. The melting of each standard causes a change in
height of the stack as each metal melts and flows (Figure 7). Force calibrati on is often

performed by balancing the force generated by the electromagnetic motor against a certified
weight added to the drive train. Length calibration can be more difficult to carry out. A
common check on the performance of the instrument is to measur e the thermal expansion of
a material whose values are accurately known (such as aluminium or copper).
TYPICAL EXPERIMENTS: This section discusses the most common types of experiments
performed using TMA,by way of introduction to some of the more advance d applications
described later. Thermomechanical Analysis
Thermomechanical measurements can be carried out on a wide range of solid samples. The
most usual mode of measurement is either in compression (for self -supporting samples) or
tension (for thin films and fibres). Some materials exhibit anisotropic behaviour
(particularly films or crystals) in that changes in dimensions will differ depending upon
which axis the measurements are performed.
Thermal expansion measurements and softening temperatures. Plo ts of the change in length
of a sample of a silicone gum rubber are shown in Figure 10. Three experiments were
carried out on the material with different applied forces [1].

At zero force a change in slope of the curve can be seen around –60°C due to the sample
undergoing a change from glassy to rubbery behaviour. At this temperature the polymer
chains acquire additional degrees of mobility which is seen as an increase in thermal
expansion coefficient. The glass transition temperature (Tg) can be defined by finding the
intercept of tangents to the linear portions of the length versus temperature plot above and
below this region. When a force is applied to the specimen the probe deforms the material
in inverse proportion to its stiffness. Below Tg the polymer is rigid and is able to resist the
applied force therefore its deformation is negligible. Above Tg the polymer becomes soft
and the probe penetrates into the specimen. The temperature at which this occurs is called
the materials’ softening temperature and is highly dependent on the force applied to the
sample.
Measurements of thermal expansion coefficients are useful in assessing the compatibility of
different materials for fabrication into components. Mismatches in behaviour can causes
stresses to build up when temperature changes occur resulting in eventual weakening and
failure of the structure. Many crystalline materials can exist in a number of polymorphic
forms which are stable at different temperatures. The transition between crystal structures is
usually accompanied by a change in density and thermal expansion coefficient which can be
detected by TMA.
Supporting information from differential scanning calorimetry is often useful in
interpreting information from TMA – particularly when softening point determinations are

made – since loss of mechanical integrity can occur due to melting, which gives an
endothermic peak in DSC or a glass-rubber transition, which causes a step change in heat
capacity.
Dynamic force thermo mechanical analysis. Half way between conventional

thermomechanical analysis and dynamic mechanical analysis is the technique of dynamic
force (or load) TMA. This method uses a standard TMA instrument but the force is changed
between two values in a stepwise (or sometimes sinusoidal) fas hion. The dimensional
changes of the specimen are monitored as a function of time (and temperature) but no
attempt is made to determine the modulus and damping properties of the material.
An example of this is shown in Figure 11 for a carbon fibre reinforc ed epoxy resin
composite beam measured in three point bending mode. The force on the probe was
changed between 0.5 and 1.5 N and back every 12 s during the measurements. The average
position of the sample deflection corresponds to a conventional TMA experi ment under a
force of 1 N. Above 90°C the epoxy resin undergoes a glass -rubber transition and the
specimen begins to deform under the applied load. The peak to peak amplitude of the probe
movement is proportional to the compliance (=1/stiffness) of the sam ple. This confirms that
the sample is softer (more compliant) above Tg. It is possible to calculate the complex
modulus of the material from the geometry of the sample, configuration of the test, applied
forces and change in dimensions, although such measu rements are best carried out using a
dynamic mechanical analyser where this is done automatically.

Some instruments are able to change the force on the sample during measurement so as
generate force-displacement curves in a manner similar to a conventio nal extensometer with
the additional advantage of good control of specimen temperature. As the stress on the
specimen is increased the material may creep under the applied load. When the force is
removed the sample may attempt to recover its original dimen sions (stress relaxation). Such
tests are useful is assessing the resilience of materials such as rubber gaskets, O -rings and
the like. This behavior is related to the time and temperature dependent visco elastic
properties of the material discussed in the next section.
APPLICATIONS:
The following examples are used to demonstrate the broad range of applications of thermo
mechanical and thermo electrical measurements. Many of the applications are not typical of
the routine types of tests described earlier, but are placed here to show the diversity of
these techniques in characterizing materials and provide short “case studies” which present
the methods in the context of addressing particular problems.
Thermo mechanical Analysis: Whilst thermo mechanical measurements are routinely used
to investigate mechanical stability and measure thermal expansion coefficients. Two
examples are given which illustrate the use of the technique on the small scale as a micro -
analytical tool to identify the distribution of two materials within a matrix and also on a
larger scale to investigate the firing of a ceramic material.
Localised thermo mechanical analysis of pharmaceuticals. Micro-thermal analysis is
discussed further. Here the technique is employed to illustrate the use of thermomechanical
measurements on small samples to identify different components in a mixture of two
materials [6]. Figure 19 shows a

Micrograph of the surface of a tablet pressed from a mixture of benzoic acid and salicylic
acid which is used as a test specimen for dissolution studies to mimic the effect of digestion
within the gut. The image was obtained by using an atomic force microscope which uses a
fine stylus to measure the height of the sample as the tip of the stylus is scanned over the
surface of the specimen. Having obtained the image, the tip may be placed on the sample
with a pre-set force and heated by passing a current through it. At the same time its vertical
displacement is measured. In this way, thermo mechanical analysis of areas less than 5 µm
square may be carried out. Several different locations may be measured consecutively and
used to “map” the softening or melting behaviour of a specimen with high spatial
resolution.
Figure 20 shows the results of carrying out such measurements at different points marked in
Figure 19. It is evident that the material examined at points 1 & 3 has a lower melting
temperature than the other locations. Since benzoic acid melts at 122°C and salicylic acid
melts at 159°C, the results from such measurements are sufficient to identify the
distribution of these materials within the image.
Rate controlled sintering of ceramics: The compaction and sintering of high temperature
refractory materials may be studied by thermo mechanical analysis. In many cases it is
desirable that the ceramic changes in dimensions in a uniform manner. In order to achieve
this the rate of heating can be controlled by the rate of change of dimensions of the
specimen. This can be done by heating the sample at a fixed heating rate an d then stopping
heating when the rate of change of length exceeds a certain limit. The process is allowed to
continue isothermally until the rate falls below the limit and then heating is recommenced.
An alternative approach is illustrated in Figure 21. He re, heating takes place at a maximum

fixed rate of temperature rise (2°C min -1) until the rate of shrinkage reaches a pre-set
value. Thereupon the rate of temperature change is controlled so as to maintain a constant
rate of shrinkage. The desired rate of shrinkage may be changed during the experiment
between different values (in this case stepped alternately between 1 and 2 µm min -1 during
the temperature rise) so as to explore the relationship between the sintering kinetics and
temperature.
A similar technique has been described for DMA whereby the temperature program was
controlled by constraining the rate of change of mechanical properties (e.g. storage
modulus) to within certain limits. This approach was shown to be effective in resolving the
multiple glass transitions of a polymer blend [8].
SOLVED PROBLEMS
94) ESCA gives sufficient chemical information up to a depth about ------------
Armstrong in polymers
a) 5-20 b) 40-100 c) 15-40 d) 100-200
95) ESCA gives sufficient chemical information up to a depth about -------------
Armstrong in metals.
a) 5-20 b) 15-40 c) 40-100 d) 100-200
95) What is thermomechanical analysis used for ?
Whilst thermo mechanical measurements are routinely used to investigate mechanical
stability and measure thermal expansion coefficients. Two examples are given which
illustrate the use of the technique on the small scale as a micro -analytical tool to identify

the distribution of two materials within a matrix and also on a larger scale to investigate the
firing of a ceramic material.
97) What are thermo mechanical properties?
Here the technique is employed to illustrate the use of thermomechanical measurem ents on
small samples to identify different components in a mixture of two materials. Several
different locations may be measured consecutively and used to “map” the softening or
melting behaviour of a specimen with high spatial resolution.
02-02-02: DYNAMIC MECHANICAL ANALYSIS (DMA)
Dynamic Mechanical Analysis (DMA) is concerned with the measurement of the
mechanical properties (mechanical modulus or stiffness and damping) of a specimen as a
function of temperature. DMA is a sensitive probe of molecular mobility within materials
and is most commonly used to measure the glass transition temperature and other
transitions in macromolecules, or to follow changes in mechanical properties brought about
by chemical reactions.
For this type of measurement the specimen is subjected to an oscillating stress, usually
following a sinusoidal waveform:
σ (t) = σmaxsin ωt ( 3)
where σ (t) is the stress at time t, σmax is the maximum stress and ω is the angular
frequency of oscillation. Note that ω =2πƒ where ƒ is the frequency in Hertz.
The applied stress produces a corresponding deformation or strain (ε) defined by:
ε = (change in dimension)/(original dimension) = Δ l / lo (4)
The strain is measured according to how the stress is applied (e.g. compression, tension,
bending, shear etc.). Strain is dimensionles s, but often expressed in %.
For an elastic material, Hooke’s law applies and the strain is proportional to the applied
stress according to the relationship:
E = dσ/dε (5)
Where E is the elastic, or Young’s modulus with units of N m-2 or Pa. Such measurements
are normally carried out in tension or bending, when the sample is a soft material or liquid
then measurements are normally carried out in shear mode, thus a shear modulus (G) is
measured. The two moduli are related to one another by:
G = E/(2 + 2v) (6)
where v is known as the Poisson’s ratio of the material. This normally lies between 0 and
0.5 for most materials and represents a measure of the distortion which occurs (i.e. the
reduction in breadth accompanying an increase in length) during testing.
If the material is viscous, Newton’s law holds. The specimen possesses a resistance to
deformation or viscosity, η, proportional to the rate of application of strain, i.e.:
η = dσ /(dε/dt) (7)
The units of viscosity are Pa s.

A coil spring is an example of a perfectly elastic material in which all of the energy of
deformation is stored and can be recovered by releasing the stress. Conversely, a perfectly
viscous material is exemplified by a dashpot, which resists extension with a force
proportional to the strain rate but affords no restoring force once extended, all of the
deformation energy being dissipated as heat during the loading process. In reality, most
materials exhibit behaviour intermediate between springs and dashpots – viscoelasticity.
If, as in the case of DMA, a sinusoidal oscillating stress is applied to a specimen, a

corresponding oscillating strain will be produced. Unless the material is perfec tly elastic,
the measured strain will lag behind the applied stress by a phase difference (δ) shown in
Figure 2. The ratio of peak stress to peak strain gives the complex modulus (E*) which
comprises an in-phase component or storage modulus (E’) and a 90° out-of-phase
(quadrature) component or loss modulus (E”).
The storage modulus, being in-phase with the applied stress, represents the elastic
component of the material’s behaviour, whereas the loss modulus, deriving from the
condition at which dε /dt is a maximum, corresponds to the viscous nature of the material.
The ratio between the loss and storage moduli (E ”/E’) gives the useful quantity known as
the mechanical damping factor (tan δ) which is a measure of the amount of deformational
energy that is dissipated as heat during each cycle. The relationship between these
quantities can be illustrated by means of an Argand diagram, commonly used to visualise
complex numbers, which shows that the complex modulus

is a vector quantity characterised by magnitude (E*) and angle (δ) as shown in Figure 3. E’
and E” represent the real and imaginary components of this vector thus:
E* = E’ + iE" = √(E'2 + E"2 ) (8)
So that:
E’ = E* cos δ (9)
And
E" = E* sin δ ( 10)
Intrumentation:
Dynamic Mechanical Analysis:
The distinction between a thermomechanical analyser and a dynamic mechanical analyser is

blurred nowadays since many instruments can perform TMA -type experiments. The
configuration of a DMA is essentially the same as the TMA shown in Figure 5 with the
addition of extra electronics to apply an oscillating load and the ability to resolve the
resulting specimen deformation into in-phase and out-of-phase components so as to
determine E’, E” and tan δ. The facility for sub-ambient operation is more common on a
DMA than a TMA. The same recommendations about modest rates of temperature change
are even more important for the larger samples used in DMA. Stepwise -isothermal
measurements are often carried out for multiple frequency operation. In this experiment the
oven temperature is changed in small increments and the sample allowed to come to

thermal equilibrium before the measurements are made. The frequency range over which
the mechanical stress can be applied commonly covers 0.01 to 100 Hz. The lower limit is
determined by the amount of time that it takes to cover enough cycles to attain reasonable
resolution of tan δ (10 s for one measurement at 0.01 Hz – though normally some form of
data averaging is applied meaning that a measurement at this frequency can take a minute
or more). The upper limit is usually determined by the mechanical properties of the drive
system and clamps.
Different clamping geometries are used to accommodate particular specime ns (Figure 8).
Single or dual cantilever bending modes are the most common for materials which can be
formed into bars. Shear measurements are used for soft, thick samples. Films and fibres are
usually mounted in tension with loading arranged so that the s ample is always in tension.
Torsion measurements are normally done with a special design of instrument since most
DMA's can only exert a linear rather than a rotational force.
The effect of temperature on the mechanical properties of a liquid can be invest igated using
a special type of dynamic mechanical analyser called an oscillatory rheometer. In this
instrument the sample is contained as a thin film between two parallel plates. One of the
plates is fixed while the other rotates back and forth so as to su bject the liquid to a shearing
motion. It is possible to calculate the shear modulus from the amplitude of the rotation and

the resistance of the sample to deformation. Because the test is performed in oscillation, it
is possible to separate the shear modulus (G) into storage (G’) and loss modulus (G”) by
measuring the phase lag between the applied strain and measured stress. Other geometries
such as concentric cylinders or cone and plate are often used depending on the viscosity of
the sample.
An alternative method for examining the dynamic mechanical properties of liquids is to

coat them onto an inert support (typically a glass fibre braid). This measurement is termed
Torsional Braid Analysis and does not provide quantitative modulus measurements since it
is difficult to decouple the response of the substrate from that of the sample.
The method of calibration of DMA's varies from instrument to instrument and it is essential
to follow manufacturer's recommendations. Temperature calibration can sometimes be d one
as for TMA's since many instruments can operate in this mode. Load or force calibration is
often carried out using weights. It is difficult to achieve the same degree of accuracy and
precision in modulus measurements from a DMA as might be obtained by using an
extensometer without taking great care to eliminate clamping effects and the influence of
instrument compliance (which can be estimated by measuring the stiffness of a steel beam).
Extensometers are much bigger instruments and the size of test spe cimens is
correspondingly larger. Additionally, they often only operate at room temperature. For
many applications the user is, however, mainly interested in the temperatures at which
changes in mechanical properties occur and the relative value of a mater ial’s properties
over a broad range of temperatures.
TYPICAL EXPERIMENTS:
Dynamic mechanical analysis is routinely used to investigate the morphology of polymers,

composites and other materials. The technique can be particularly sensitive to low energy
transitions which are not readily observed by differential scanning calorimetry. Many of
these processes are time-dependent and by using a range of mechanical deformation
frequencies the kinetic nature of these processes can be investigated.
Single frequency temperature scans. The most common DMA experiment is simply to
measure the storage modulus (E’) and mechanical damping factor (tan δ) against
temperature at a single oscillation frequency. An example of this type of measurement is
shown in Figure 12 for a specimen of the aliphatic polyester, polycaprolactone. This
polymer is typically highly crystalline and melts around 50 -60°C. However, the sample is
not completely crystalline and contains

a small amount of amorphous material which undergoes a glass -rubber transition at -40°C.
For DMA and DETA work the glass transition is often called the alpha (α) transition and all
lower temperature transitions are given corresponding Greek symbols beta (ß), gamma (γ)
etc. The peaks in tan δ at -85°C and -130°C correspond to the ß and γ transitions in the
polymer respectively and are due to the motion of short lengths of the polymer backbone
rather than the large scale increase in mobility that accompanies the glass -rubber transition.
It is very difficult to measure this type of behaviour by DSC, but the size and position of
these transitions are often very important for a polymer’s impact properties since they
provide a means of dissipating mechanical energy as heat.

Figure 13 shows plots of storage modulus and damping factor for poly(ethylene
terephthalate) (PET) film against temperature. The measurements were performed at a
number of mechanical oscillation frequencies (0.3 – 30 Hz) and were carried out in a step-
wise isothermal fashion with the temperature of the oven being raised by 5°C and allowed
to come to equilibrium before each frequency was successively applied to the specimen. It
can be seen that the peak in tan δ moves to a progressively higher temperature as the
measurement frequency is increased as a consequence of the time dependence of the glass-
rubber transition. This maximum reflects the temperature at which the material can deform
within the same time frame as the mechanical oscillation. Below this temperature the
material is too sluggish to react to the deformation and behaves as a solid, above this
temperature the material relaxes faster than the deformation and behaves as a viscous
liquid.
Time-temperature super position. It is well established that the observed temperature at
which the glass-rubber transition occurs depends upon the timescale over which one
investigates molecular mobility (this applies to all methods of determining this parameter).
To a first approximation the process can be treated as a simple thermally activated effect
and the relationship between the temperature of maximum mechanical damping (Tpeak) and
the timescale (or
frequency (f) of the applied forcing variable (in this case mechanical deformation) can be
analysed using a simple Arrhenius expression:
ln(f) = ln(A) – Ea/(R Tpeak) (16)
where Ea is the apparent activation energy for the process and R is the gas constant.

A more rigorous approach recognises that the glass -rubber transition is a co-operative effect
and does not conform to the simple model described above. A co mmon method for treating
such a response is to superimpose data collected at different temperatures and frequencies
onto one smooth curve. In Figure 14 the data from Figure 13 are presented on a frequency
axis. It can be seen that if a curve at one tempera ture is chosen as a reference point then
data from other temperatures can shifted in frequency to produce a smooth continuous
change in properties spanning a wide frequency range. Ideally both the moduli and damping
factor data should produce good overlays (Figure 15). The relationship between the
frequency shift (a) at a specific temperature (T) and the reference temperature (Tref) is
usually expressed in terms of the Williams -LandelFerry (WLF) equation
log[a(T)] = C1(T-Tref)/(C2 + T - Tref) (17)
where C1 and C2 are constants.
Time-temperature superposition is a means of extending the frequency range of dynamic

mechanical data and has applications for the evaluation of materials for acoustic damping
properties.
APPLICATIONS:
Dynamic mechanical measurements are not limited to running experiments on samples in
air or inert gases. With care, measurements can be carried out with the test specimen
immersed in a liquid or on liquid samples themselves as the following examples
demonstrate.

Dynamic mechanical analysis of fibres under dye bath conditions.
The dyeing and washing behaviour of regenerated and synthetic fibres are markedly
dependent upon temperature. For example, acrylic fibres must be dyed above Tg in order to
facilitate dye diffusion; in contrast, the characteristic high wet fastness properties of the
resultant dyeings can be attributed primarily to the relative absence of dye diffusion that
results from such aqueous treatments (e.g. laundering) being carried out at temperatures
below the Tg of the fibre. Although the effect of temperature on the physical properties of
dry fibres is readily performed using conventional thermoanalytical techniques (e.g. DSC),
it is less easy to examine the behaviour of fibres under dye bath conditions ow ing to the
presence of water. Of particular interest is the effect of “carriers” - additives to the dye bath
which are used to accelerate the rate of dye diffusion within the hydrophobic fibres. The
mechanism by which these materialsenhance dye uptake is t hought to be by plasticising the
fibre by reducing its glass-rubber transition temperature and thus increasing the segmental
mobility of the polymer chains. Using a dynamic mechanical analyser, it is possible to carry
out experiments with the sample immersed in a liquid. For this type of measurement, the
instrument is fitted with a metal liner which is inserted into the oven so that the sample and
clamps can be immersed and the temperature of the bath programmed in the usual way.
Results from testing acrylic fibres under different conditions are shown in Figure 22.
It can be seen that peak in damping factor is reduced from around 90°C to 72°C by the
presence of water. Addition of benzyl alcohol to the water bath (as a model “carrier”)

further depresses and broadens the peak in tan δ in a fashion typical of the action of a
plasticiser thus confirming the nature of carrier activity [9].
Variable temperature oscillatory rheometry of food additives. Cellulose ethers, such as
methyl cellulose, are widely used as thickening agents in a variety of foodstuffs such as pie
fillings and potato croquettes. These substances possess the unusual feature of forming a
reversible gel structure on heating which serves to maintain the mechanical integrity of the
product during baking. On cooling, the gel structure breaks down and the original texture of
the mixture is regained.
Measurements on a 10% solution of methyl cellulose in water were carried out using an
oscillatory rheometer. Plots of storage and loss moduli (G’ and G ” respectively) against
temperature are shown in Figure 23. Below 55°C the loss modulus is higher than the
storage modulus indicating that the specimen is responding more like a liquid than a solid.
Above this temperature, the situation is reversed and the specimen has predominantly solid-
like characteristics. The cross-over between G’ and G” corresponds to the formation of a
cross-linked gel network and the transition between the two types of behaviour [10]. The
effect of different additives on gel formation can be a useful indicator of synergistic
(lowering of gel temperature) or antagonistic (raising of gel temperature) interactions
between materials.
DMA is regularly used to study the chemical reactions which lead to cross -linking of
thermosetting resins, such as those used in the manufacture of composites. At high degrees

of network formation the rubbery cross-linked gel will vitrify into hard glassy material and
the storage modulus will increase by several orders of magnitude. Plotting gel point and
vitrification point against temperature and time leads to a TimeTemperature -Transformation
(or Gillham-Enns [11]) diagram which can be used to map out the curing of thermosetting
polymers. The use of dielectric analysis in the following section will show how this
technique can also be used to follow chemical cross -linking and the reverse effect of
breakdown of molecular structure brought about by exposure to UV radiation.
ESCA: ELECTRON SPECTROSCOPY FOR CHEMICAL ANALYSIS:
Electron Spectroscopy for Chemical Analysis, also known as X-ray Photoelectron

Spectroscopy (XPS), provides information on the atomic composition and chemical bonding
of a sample on the surface (top few nanometers). ESCA can detect all elements except for
hydrogen and helium, and the detection limit is about 0.1 atomic percent. We can use ESCA
on both conductive and insulating samples, which mean this technique has a wide
application for both organic and inorganic samples.
How it Works: In Electron Spectroscopy for Chemical Analysis (ESCA), we use an X-ray
beam to bombard the surface of sample so we can measure the core electrons emitted. We
have multiple types of excitation sources: a non -monochromatic Al or Mg x-ray and a
monochromatic Al x-ray source. The choice of source is based on the samp le under analysis
and what information is needed about the sample. The X -ray beam penetrates several
microns into the sample. When this occurs, core electrons from the atoms of the samples are
freed, but only the electrons from the near surface region (top few nanometers) can leave
the surface. The instrument collects and measures the kinetic energy of these electrons from
which we can calculate the binding energy, which originally held the electron to its source
atom. From the binding energy we can determi ne which element the electron came from and
determine the oxidation state (chemical binding state) of that atom (for many elements). An
argon ion sputter gun can be used to remove the surface layers of the sample and monitor
changes in elemental composition relative to depth. Since the escape depth for low-energy
electrons is only 1-10 nm, ESCA is very surface-sensitive. We also perform “small spot
ESCA”, which refers to the ability of the electron analyzer to aperture down to an area as
small as 75 microns in diameter. When we combine this feature with a high -strength but
small X-ray source, we are able to provide a chemical analysis of features smaller than 100
microns in width.
ESCA Applications Include:
A) Materials Evaluation:
• Oxidation states
• Identification of polymeric coatings
• Surface compound identification
• Surface composition

• Plasma treatment
• Anti-reflection coatings
B) Failure Analysis: • Corrosion product • Material delamination • Discoloration of epoxy •
Chemical degradation of surfaces • Catalyst poisoning.
C) Quality Control: • Identification of organic contamination • Breakdown of surface
lubricants • Chemical degradation of surfaces • Adhesion failures.
Data Presentation: We usually plot ESCA spectra as the counts (number of ele ctrons) versus
electron binding energy. Using curve-fitting software, we can determine the oxidation state
of the sample surface by interpreting binding energy shifts. The elemental composition of
the sample surface can be determined by a “survey” spectrum, which usually includes a
wide range scan from 0 eV to 1100 eV. Additionally, a “high resolution” spectrum can be
used to discern subtle peak shape and peak energy changes. These high -resolution spectra
usually cover a narrower energy range.
Sample Constraints: An ESCA sample can be up to 60mm in diameter x 13 mm high in size.
We can analyze insulators, thin films, powders and organics. The sample must be non -
volatile and be compatible with ultra high vacuum in the range of 10^ -7 to 10^-10 Torr.
XPS PRINCIPLE AND INSTRUMENTATION: X-RAY PHOTO ELECTRON SPECTROSCOPY
Introduction:
X-ray photoelectron spectroscopy (or XPS) belongs to the group of surface analysis
methods wherein the sample under investigation is bombarded with
photons/electrons/ion/etc. for exciting the emission of photons/electrons/ion/etc.
XPS involves irradiating the sample with low energy ((~1.5 keV) X -rays such that
photoelectric effect is induced. An electron spectrometer with high resolution records the
energy spectrum of emitted photoelectrons. Highest available vacuum conditions are
required for XPS experiments. High vacuum assists photoelectron transport to the analyzer,
and also avoids recontamination of clean samples. Contamination is an important concern
in XPS, since it is a surface sensitive technique and the sampling depth is usually a few nm
Principle:
Surface analysis by XPS involved irradiation of the sample by low -energy (and mono-
energetic) x-rays and the subsequent analysis of the energy of emitted electrons. Typically
used x-rays are Kα lines of Mg (1.2536 keV) and Al (1.4866 keV). The penetration depth of
these photons in solids is limited to a few microns. Thus, interactions take place between

the incident photons are the surface atoms leading to the photoelectric emission of
electrons. The kinetic energy (K.E.) of the emitted electrons is expressed as:
K.E. = hν – B.E. – φs (1)
here hν is the energy of the photon, B.E. is the binding energy of the atomic orbital from
which the electron is released, and φs, is the work function of spectrometer. B.E. can also
be described as the energy difference of the initial and final states when an electron is
released from the atom. Electrons emitted from an ion possess differ ent kinetic energies
owing to the possibilities of different final states of the ion from each type of atom.
Besides, there exists different probability or cross -section for each of thefinal state. Figure
1 shows relative B.E. and ionization crosssections for an atom.
Binding Energy:
In a photoemission process, the total energy of the system, before emission, is equal to the
sum of the energies of incident X-ray photon (hυ) and target atom in its initial state (Ei).
After emission, total energy of the system equals the sum of the K.E. of the emitted
electron (Ek) and energy of ionized atom in its final state (Ef). Equating the total energy
before and after emission and comparing with Einstein’s equation gives the B.E. as the
energy difference between the final and initial states of the target atom (i.e., Ef - Ei). In
figure, Fermi level corresponds to zero B.E., and the depth below it reflects the relative
energy of the ionized atom after emission, or simply B.E. of electron. Relative probabilities
of different ionization processes are indicated by the length of the lines. Ionization causes
splitting of the levels p, d and f, creating vacancies in p1/2, p3/2, d3/2 d5/2, f5/2 and
f7/2.Thesplitting ratio of spin-orbit is 1:2 for p, 2:3 ford and 3:4 for f levels. For
instance,Figure 2 shows the spin-orbit splitting in Si 2p level.
XPS analysis relies on the fact that each element possesses a unique set of B.E. Thus, the
concentration of elements at the surface can by identified and determined. B.E. of elements
vary (the chemical shifts) because of differences in the chemical potential and polarizability

of compounds. These shifts lead to the identification of chemical state of the material under
investigation. The excited ions left after photoemission, may also eject Auger electrons.
Auger emission typically occurs after 10-14 s of the photoelectric emission. Another
competing emission of a fluorescent X-ray photon may also take place. Schematic
illustration of Auger phenomenon is shown in Figure 3, where an electron from outer shell
occupies the vacancy in the inner orbital by emitting a second electron in the process. This
second electron carries the extra energy, and is called the Auger electron. The K.E. of Auger
electron is the energy difference between the initial ion and the doubly char ged final ion.
Additionally, the K.E. of Auger electron does not depend on the mode of initial ionization.
Therefore, photoionization often generates two electrons: one photoelectron and another
Auger electron. The sum of the K.E. of theemitted electrons c annot be larger than that of
the ionizing photons.
Figure 3: Top XPS emission for a hypothetical atom where an incident photon ejectsa
photoelectron.
Electrons undergo far more interactions with matter than photons, this results in extreme
short path length of electrons (~ few angstroms) in comparison to photons (~ few microns).
Therefore, when the depth of ionization is of the order of few microns, the electrons
originating from deep into the bulk of solid (i.e., at a distance more than few angstroms
from the surface), experience high energy losses. However, the electrons originating from
the surface (or upto a depth of few angstroms from the surface) do not lose their energy,
and cause peaks in the XPS spectrum. These electrons are crucial in XPS analyse s. The
deeper electrons experience elastic loss process before releasing from the background .
Factors affecting the intensity of peaks in the spectrum:
Consider a volume element of the sample with thickness dz at a depth z underits surface.
The photoelectrons emitted at an angle θ with respect to the normal to the sample surface
(the “photoemission angle”) enter the detector and contribute to the spectrum. Usually, X -

rays’reflection and refraction induced photoelectrons are significant only at a grazing ang le
φ < 5º, and may be ignored in other cases
X-ray flux is not usually known.Therefore, this factor is not considered and peak intensity
ratios or composition of the sample in terms of atom percent (considering one peak from
each chemical element) is taken into account. The extent to which volume element
generates counted photoelectrons is influenced by the particular geometry of the
experimental setup. The following cases may normally arise:
1) More surface is irradiated by X -rays than detectable by the analyzer optics (e.g., a
non-monochromated X-ray source may have been used)
2) Less surface isirradiated by X-rays than observed by the analyzer optics (using a
monochromated Xray source)
Both these cases must be considered carefully and sometimes a transition b etween the two
cases may be observedwhen there is a change in photoemission angle θ. However, these
geometrical factors can be cancelled by evaluating sample composition as atomic
percentage.
The analyzer acceptance angle Ω0 is a function of the lens progr ams and aperture settings,
and is unknown. This is also cancelled byevaluating sample composition as atomic
percentage(consideringpeak intensityratios).

The attenuation of emitted photoelectrons flux gives XPS its surface sensitivity. The
inelastic mean free path is the average distance between collisions where the photoelectron
loses its energy. If a photoelectron loses K.E. in a collision, it will contribute to the
background rather than to the characteristic “no -loss” peak in the spectrum.
Instrumentation:
The instrumentation of XPS system can be explained using the experimental set up shown
in fig. 10. In a typical set up, when the sample kept in ultra-high vacuum is illuminated by
the photons with energy (hν); soft x-rays, then after direct transfer of energy from the
photons to the core level electrons their atoms on the surface emit electrons or sp called
photoelectrons. The process can be explained as follows:
1. A bound electron adsorbs a photon and converts part of the energy to kinetic energy. 2.
While leaving the atom, some energy of the electron is consumed in overcoming the
Coulombic attraction of nucleus, thereby decreas ing its kinetic energy. 3. At this time the

outer orbitals readjust, reducing the energy of the final state which is being created and
delivering this extra energy to the outgoing electron. 4. Then the XPS spectrum is obtained
by determining the K.E. and number of electrons escaping from upper 0 to 10 nm of sample
under investigation. 5. XPS may be routinely employed to study inorganic compounds
including metal alloys, semiconductors, polymers, glasses, ceramics, ion -modified
materials, etc.
SOLVED PROBLEMS 02
1. Which of the following is the detection limit of ESCA?
a) 0.1% monolayer
b) 0.5% monolayer
c) 1% monolayer
d) 2% monolayer
2. By studying which of the following can we determine if the surface corresponds to

C-O or C=O chemical form?
a) Mass of the electron

b) Energy of the carbon peak
c) Binding energy
d) Charge of electron
3. What is the excitation potential?

The minimum energy required to eject an electron from an atomic shell is known as
excitation potential (Ec). As the size of the atom increases (e.g., from light to heavy
elements), the energy required to excite any particular transition line also increases.
For instance, Ec for Ni Kα is much higher than that for Al Kα. The excitation potential
of K shell is higher than other shells. In addition, the excitation potential of K shell
increases extensively with a small increase in the atomic number.
4. What is the x-ray range?

X-ray range is the depth of x-ray production within the interaction volume. It mainly
depends on the beam energy, critical excitation energy, and the specimen density.
02-02-03: X-RAY PHOTO ELECTRON SPECTROSCOPY

As explained in the section “Photoelectric effect” and depicted in the figure, in XPS an
incident x ray (of energy hf, f being the frequency) knocks an el ectron (with binding energy
BE) out of the atom which escapes with an energy equal to E = hf – BE – Φ, where Φ is the
work function of the spectrometer (of the order of a few eV). Knowing Φ, the energy of the
incident x ray and capturing the electron to me asure its kinetic energy allows the
determination of the binding energy of the electron and thus the identification of the

element. The figure below (from Dr. B. Vincent Crist) shows a beautiful description of the
complete XPS process from x ray irradiation to compilation of the electron energy spectra.
XPS is used to study the elemental composition, chemical state and electronic state of a
material. Normally it helps to explore the top 10 nm or top 20 layers of a surface. To avoid
scattering of the XPS electrons with air, XPS is performed in a ultra-high vacuum (UHV)
chamber. Samples can be studied without any preparation other than normal cleaning, but
some applications can benefit from being sputtered with ions to clean off surface
contamination.
XPS can detect elements starting from Li (Z=3) and higher; hydrogen (Z = 1) and helium (Z
= 2) cannot be detected due to the low probability of electron emission. Detection limits for
most of the elements are in the parts per thousand range, but it can be increase d to parts per
million (ppm) for large concentrations or through long collection times (overnight). XPS is
applicable to inorganic compounds, metals, semiconductors, organic material, bio -
materials, as well as oils and gases under special conditions. XPS i s non-destructive and
can be safely used in the study of works of art.
XPS Spectra:
Once the XPS electrons are captured and their kinetic energy measured, the binding energy
of the electron can be estimated and used to produce the XPS spectrum, which is a
histogram of the number of electrons captured as a function of their binding energy. Since
the binding energy is different for every atomic energy level, the electron energy spectrum
will show peaks at these levels and, depending on the energy resolution of the electron
detector (usually of the order of an eV or smaller), at the sublevels within shells. The
notation used in XPS to identify the energy levels follows the standards set by quantum
mechanics. As mentioned in Chapter One, the binding energy of a n atomic electron depends
not only on the energy shell of the level they occupy, but also on the magnetic interaction
between its intrinsic spin and the orbital angular momentum. Thus the energy levels are
characterized 51 by the orbital, and total and orb ital angular momentum quantum numbers,
N, j and l, respectively, and these are used in the nomenclature shown in the figure. The
accompanying table shows the most common energy states encountered in XPS.
Chemical shifts:
The possibility of determining accurate electron binding energies allows XPS to quantify
small variations of binding energy due to, for instance, the binding of the atom to another
atom (e.g. such as in the formation of compounds). Such variations are known as chemical
shifts and produce small changes in the location of the peak positions; in oxidation, for
instance, atoms lose electrons which in turn increase the binding energy of the
photoelectron. XPS is specially suited for detecting the chemical shifts due to the fact that,
being a one-electron process, the emitted 54 electrons have a very small energy dispersion,
especially in comparison to other processes, such as Auger emission. One example is

titanium which exhibits a very large chemical shifts between different oxidation states. Th e
figure shows the electronic configurations of both neutral Ti and O as well as of TiO2 with
the titanium atom losing 4 electrons and the two oxygen atoms receiving them. The lower
panel shows the spectrum from a pure Ti sample (Ti0 ) compared with that o f titanium
dioxide (Ti4+); as it can be observed, the energy shifts are 4.5 eV for the 2p1/2 and 4.95 eV
for the 2p3/2. A more quantitative example of the change in binding energy due to oxidation
is illustrated in the XPS spectra of fluorine attached to a silicon surface forming layers of
SiF1, SiF2 and SiF3. The left panel of the figure shows the spectra of SiFx showing the
shifted peaks, and the right panel presents the energy shift for four oxidation states. Again,
oxidation (i.e. the removal of a valence electron) increases the binding energy, while the
addition of an electron decreases the binding energy. The ability of XPS to resolve chemical
shifts depends mainly on the magnitude of the shift, the sharpness of the incident radiation
as well as on the energy resolution of the electron detector. Samples with various
components that overlap their photoelectron binding energies produce broad XPS peaks,
which cannot be resolved for chemical shifts. Chemical shifts are usually in the range of a
fraction of an eV to about 10 eV.
XPS Sampling Depth :
The XPS process is obscured by a several factors, but most importantly by the absorption
properties of the material both for the incident x rays and the emitted electrons; although
the penetration depth of an x ray is of several μm, the mean free path of an electron is of
the order of a few nm, thus strongly limiting the sampling depth of XPS. An accurate
description of the 55 absorption of electrons by the medium is a complex process that
depends on the kinetic energy of the photoelectron and the properties of the material; in
practical terms it is best to describe such absorption in terms of a phenomenological
attenuation law known as the Beer-Lambert law. In an XPS analysis the x rays free a
number of electrons a depth d below, a fraction of which will move straight to the surface.
If the number of electrons that move toward the surface per unit time is Io, the number of
electrons that will reach the surface per unit time, IS, will be given by IS = I0 e -d/λ ,
where λ is the electron mean free path in the medium. Notice that at depths of d ≈ 3λ the
intensity at the surface is IS ≈ 0.05Io, i.e. 95% of electrons produced at distances of 3λ will
be absorbed; this fact is used to define the “sampling depth” a s 3λ. Luckily, the mean free
path, λ, has a behavior that is similar for a large class of materials and can be characterized
in terms of the so-called “Universal Curve” shown in the figure (adapted from the
investigation of Seah and Dench). Experimental me asurements presented there for a variety
of media show that the sampling depth (or escape depth) of electrons is always in the range
of 3 to 30 nm or so, this puts λ in the range of 1 to 10 nm. In summary XPS can gather
information from the top 30 nm of material which corresponds to about 20 atomic layers.

Plasmon peaks:
Other effects that modify the XPS spectra are the so called plasmon peaks which are
produced by the interaction of the photoelectrons with collective excitations of the
electrons in the valence band known as plasmons.
The plasmon excitations are fluctuations of the electron density produced either by the
photoelectron itself while it propagates through the solid (extrinsic plasmon), or by the
valence electrons in response to the presence of the core hole left by the emitted
photoelectron (intrinsic plasmon). Interactions of the photoelectron with the plasmons
reduce the kinetic energy of the electron making it appear with a larger binding energy in
the XPS spectrum. Due to the repetitive spatial pattern of the plasmon waves, the
photoelectron-plasmon interactions can occur more than once producing several “plasmon”
peaks in the XPS spectrum at regular energy intervals. The figure shows the Al 2s and Al 2p
XPS peaks along with several plasmon peaks.
The energy intervals of the plasmon “satellite” peaks are dictated by the material and can
provide useful chemical information. Plasmons are noticeable mainly in Al, Mg and Si and
are absent in nonmetals. A similar effect is produced when the photo electron excites a
valence electron into a higher energy level (i.e. it “shakes up” the electron). As before, the
electron kinetic energy is reduced and the electron is counted in the spectra as with a larger
binding energy. Due to the narrowness of the valence energy band, these shake ups tend to
reduce the kinetic energy by a fixed amount thus producing regular distinct “shake up”
peaks at binding energies a few eV larger than the real one. A related effect occurs when the
photoelectron kicks out a valence electron (“shake off”). Since such inelastic collisions can
reduce the electron kinetic energy by a wide range of energies, in the end the electrons
appear at apparent larger binding energies –not a series of narrow peaks as before— but in a
broad “shake off” peak.
Static charging:
Yet another phenomenon that can affect the XPS spectrum arises due to the possible build
up of positive charge on the surface of non-conducting samples. When thousands of
photoelectrons are emitted and the sample is non -conducting, an excess of positive charge
is created on the surface of the sample which, in turn, creates a surface electric field that
will reduce the kinetic energy of the ejected electrons shifting the XPS peaks to higher
energies. Fortunately, such effect can be eliminated by shifting the spectrum according to a
well known reference point, such as the “adventitious carbon line” (C 1s line of 284.8 eV).
Other -hardware based— approaches are depositing a thin layer of gold over the sample, or
using of a low energy electron gun during the x ray irradiation to compensate the charge
deficiency.

When the sample charges negatively (due e.g. to electron backscattering), the kinetic
energy of the photoelectrons increases due to electric repulsion and thus the electrons a re
counted as with a lower binding energy. In such cases the XPS analysis is impossible.
SOLVED PROBLEMS
5. ESCA focusses on which of the following information?
a) Mass of the electron
b) Charge of the electron
c) Binding energy of the electron
d) Mass of atoms
101) Discrete electrons cannot be observed in electron ionization of an atom due
to which of the following reasons?
a) Environmental disturbances
b) Same mass
c) Same charge
d) Electron- electron interaction

102) What is x-ray spatial resolution?
X-ray spatial resolution is defined as the maximum width of the interaction
volume generated by electrons or x-rays projected up to the specimen surface. The
low atomic number and low-density specimens allow deeper and wider electron
beam penetration and generation of x-ray lines which degrades the x-ray spatial
resolution achieved.
103) What is the primary mechanism of x-ray absorption?
X-rays are primarily absorbed in specimen material by photoelectric absorption.
An x-ray photon loses all its energy to an orbital electron, which is ejected with a
kinetic energy equal to the difference in photon energy and critical ionization
energy required to eject the electron.
02-02-04: CHEMICAL SHIFTS IN X-RAY AND PHOTO ELECTRON

SPECTROSCOPY
Introduction:
I have been asked to give a review with historical emphasis of the chemical shifts in
electron spectroscopy. I will start this with a short review of the discovery an d
interpretation of the chemical shifts in X-ray spectroscopy. This effect was discovered in
the early 1920’s, and the interpretations given at this early date were essentially correct.
The effect is the same as that causing the chemical shifts in electron spectroscopy. The X-
ray spectroscopy started with the early works of Barkla, Bragg and others around 1915, and
the experimental technique was then greatly refined, particularly by Manne Siegbahn and
his collaborators in Lund and Uppsala and later in Stock holm .

With particular regard to the subject of this review, it is interesting to cite a paragraph from
Manne Siegbahn’s Nobel lecture: ’Recently, in a lecture to the Swedish society of
Chemists, I drew attention to preliminary studies which are being made in one of these new
fields - the matter of the chemical properties of the atoms having an effect upon the
phenomenon of X-radiation.’This was a great surprise at the time, since it was generally
accepted that the X-radiation was a purely atomic effect. These early discoveries seem to
have been largely overlooked by later generations of spectroscopists.
Chemical shift in X-ray spectroscopy:
When an atom is irradiated by an energetic beam of particles or photons, an electron from
an inner shell can be expelled. When the vacancy is filled by an electron from an outer
electronic shell, so called characteristic X -ray radiation can be emitted. The energy of the
radiation depends on the energy levels of the atom. If an atom is irradiated by continuous
X-rays, then the radiation can be absorbed if the energy of the incoming photon is sufficient
to ionize the atom or to excite the inner electron to an unoccupied level. This gives rise to
an absorption edge in the spectrum for each inner level.
The position of the absorption edge gives information about the electron binding energy,
i.e., the energy needed to remove the electron from the atom. One problem is here that the
edge has a certain structure, which makes the determination of the absolute binding energy
difficult. The emission spectrum, on the other hand, gives information about the difference
in binding energy between different shells – a quantity that could be determined with higher
accuracy. For several decades, X-ray spectroscopy was the main source of information
regarding the atomic structure. (For an extensive review of the early X -ray spectroscopy,
the reader is referred to the monograph.
Discovery of the chemical shift in X-ray spectroscopy:
it was discovered that the wavelengths of the X -radiation and the position of the absorption
edge depend on the chemical environment of the atom. Bergengren of the Manne Siegbahn
group at the University of Lund found in 1920 that the K-absorption spectrum was different
for different modifications of phosphorus. the same group found that the position of the X -
ray absorption edge of chlorine depends on the chemical valence . Then the chemical shift
in X-ray absorption was discovered.
Interpretation of the chemical shift in X -ray spectroscopy:
Here, the valence of the chlorine ion is +7 and of the surrounding oxygen ions -2. If a
certain charge (Q) of the central ion, assumed to be distributed uniformly on a sphere of
radius r, is removed to infinity, the potential inside that shell would be changed by Q/4π²or
– and hence the binding energy of electrons inside the shell by the same amount. In reality
the charge is mainly transferred to the surrounding ions, and assuming that these can be
represented by a uniformly charged spherical shell of radius R, the effective energy sh ift
would be

∆E = Q 4π²€0 ³1 r − 1 R ´
Since the molecular bonds are generally not purely ionic but at least partly covalent, the
effective charge is considerably smaller than the valence numbers would indicate. This
simple model gives a qualitative explanation of the shift in the binding energy and hence of
the X-ray absorption edge. Since the potential is constant inside a uniformly charged
spherical shell, this model does not provide any explanation of the shift observed in the X -
ray emission spectra.
Discovery of the chemical shift in photo-electron spectroscopy:
In studying the electron binding energy, it was soon discovered that this energy does
depend on the chemical environment of the atom studied. The first observation of that
effect was made in 1957 by Sokolowski, Nordling, and Siegbahn , where a shift of several
eV was found between metallic copper and copper oxide . The effect was even more
pronounced for elements like chlorine or sulfur, which can appear in a number of different
environments. The shift of some sulfur compounds is illustrated . Although this effect is
quite analogous to the corresponding shift in X -ray absorption, discovered more than three
decades earlier, it came as a surprise to the investigators, and the interpretation was unclear
for some time – possible surface charge was one hypothetical explanation.
The Uppsala group, Hagström, Nordberg, Nordling, was making some complementary
measurements on sulfur but was running out of the compounds normally used (sulfate or
sulfite). They knew that a sulfur compound was used in the photographic process and
therefore borrowed some salt from the photo lab. Then to their big surprise a double peak
showed up in the spectrum HNS64 [12] (see Fig.Fig:Sulfur 6, right). This effect was real
and could not be due to any (irregular) surface charge or other instrumental effect, since the
sodium 1s line was still unsplit. The salt used was thiosulfate, which contains two sulf ur
ions at different locations. It was then realized that the shift was correlated to the chemical
environment.
It is clear from these illustrations that quite detailed information about the chemical
environment can be deduced from the chemical shift in the spectrum, and this constitutes
the fundament of the ESCA method.
Calculation of chemical shifts:
The chemical shift in the ESCA spectrum – or equivalently in the X-ray spectra – is caused
by changes in the electron binding energies. Therefore, we shall here consider different
ways of calculating the electron binding energy of an atom or a mol ecule – methods that
can also be used to evaluate chemical shifts.
Single-particle picture:
More detailed calculations of electron binding energies could not be performed until the
1960’s, when sufficiently powerful computers became available. Essentially two methods
were then developed,

• The Koopmans-theorem method and
• The ∆SCF method.
In the Hartree-Fock model the binding or removal energy of an electron is according to
Koopmans’ theorem equal to the negative of the orbital energy eigenvalue
BE = −εHF.
This assumes that the remaining electrons are unaffected by the removal or in other words
that the electron relaxation is neglected. If some other SCF scheme is used, such as the
Slater exchange approximation or variants thereof, the Koopmans’ theorem is not exactly
valid, but the non-validity of this theorem is easily corrected for.
In the ∆SCF method, separate self-consistent-field (SCF) calculations are performed of the
system before and after the removal of the electron. In this way the electron relax ation is
taken into account to a considerable degree.
SOLVED PROBLEMS
104) ESCA can identify elements in the periodic table above which of the following?
a)Carbon
b) Boron
c) Helium
d) Potassium
105) ESCA gives sufficient chemical information up to a depth about ________
Armstrong in oxide.
a) 5-20
b) 15-40
c) 40-100
d) 100-200
106) Can XPS be used to defi ne fi lm thickness?
If the fi lm is less than the sampling depth and some spectral difference can be
discerned between the fi lm and the underlying substrate, then the answer is yes.
Indeed, very precise measurements can be carried out on uniform fi lms through a
modifi cation of the Beer – Lambert Law.
107) What is the fl aw in Koopman ’ s theorem when applied to examining XPS spectra?
A frozen orbital approach is used; that is, this assumes no
rearrangement/relaxation occurs for the valence electrons of the photoelectron
emitting atom/ion.
CHECK POINT 02-02
1) ESCA gives sufficient chemical information up to a depth about ________ arm
strong in polymers.
a) 5-20
b) 15-40
c) 40-100
d) 100-200

SUMMARY
The description of thermomechanical and thermoelectrical measurements in a modest
chapter such as this is an ambitious exercise. The author has attempted to cover a wide
range of methods and applications with the intention of illustrating the diversity of this
field whilst emphasizing the relationships between the static techniques (such as TMA and
TSCA) and the dynamic techniques (dynamic force TMA, DMA and DETA). With the
exception of TMA, these methods are often promoted as some of the more “advanced”
thermal analysis techniques. It is hoped that the preceding pages help to dispel this myth
without belittling their ability to measure useful properties.
The chemical shifts in X-ray spectroscopy were detected and qualitatively interpreted some
80 years ago. The corresponding shifts in core -electron spectroscopy were detected and
interpreted 40 years later. Quantitative evaluation of the core -electron binding energies and
shifts became possible when sufficiently powerful computers were available in the 1960’s.
During the past four decades a large number of more or less sophisticated computational
methods have been developed, and it is now possible to evaluate the binding energies –
including vibration levels and the satellite structure – and chemical shifts with an accuracy
of the order of 0.1 eV, also for relatively complex molecules. Therefore, the combination of
accurate experimental and theoretical investigations can now yield valuable information
about molecular structure and dynamics.
KEY WORDS
Inelastic scattering, Hard Segment, Survey spectrum,High resolution Sectrum,
REFERENCES
D.Q.M. Craig; “Dielectric Analysis of Pharmaceutical Systems”, Taylor and Francis,
London,1995
J. Goodwin and R. W. Hughes; “Rheology for Chemists: An Introduction”, Royal Society of
Chemistry, Cambridge, 2000
J. D. Ferry, "Viscoelastic Properties of Polymers," 3rd. edn., Wiley, New York, 1980
N. G. McCrum, B. E. Read and G. Williams, “Anelastic and Dielectric Effects in Poly meric
Solids”, Dover, New York, 1991
K.P. Menard; “Dynamic Mechanical Analysis: A Practical Introduction to Techniques and
Applications”, CRC Press, Boca Raton, 1999
L. E. Nielsen and R. F. Landel; “Mechanical Properties of Polymers and Composites”,
Dekker, 2nd edn., New York, 1993
Answer to Check Point 02-02
1] M. Siegbahn, Spektroskopie der Röntgenstrahlen (Springer, Berlin, 1931).
[2] A. Lindh, Z. Phys. 6, 303 (1921)
[3] J. Bergengren, Z. Phys. 3, 247 (1920).
MOOCS
____

YOUTUBE VIDEOS
https://www.youtube.com/watch?v=UjiirGWKfoA
https://www.youtube.com/watch?v=lKNOfuW_M3A
WIKIPEDIA
OER
____
REFERENCE BOOKS
2001.
3. C.Duval, Inorganic Thermogravimetric Analysis, Else vier Amsterdam, 1962.
1965.
5. W.W. Wandlandt , Thermal Analysis, Wiley , New York , 1986.
6. A.Blazek, Thermal Analysis, Van Nostrand Reinhold , London ,1972 .
7. H.Gunzzler and A.Williams , Hand Book of Analytical Techniques, Wiley – VCH ,
Weinheim , Vol -2, 2001. 8. G.W.Ewing , Analytical Instrumentation Handbook, Marcel
Dekker Inc, New York, 1990.

CREDIT 02-UNIT 03: DESCRIPARION OF ESCA SPECTROMETER
LEARNING OBJECTIVES
 Explain the working of ESCA-spectrometer
 Implement the principles and operating condition of the instruments.
 Explain different types of Instrumental methods
 Perform the chemical analysis by using Spectrophotometer
 Differentiate between classical and instrumental methods of chemical analysis
INTRODUCTION
Electron Spectroscopy for Chemical Analysis, also known as X -ray Photoelectron

Spectroscopy (XPS), provides information on the atomic composition and chemical bonding
of a sample on the surface (top few nanometers). ESCA can detect all elements except for
hydrogen and helium, and the detection limit is about 0.1 atomic percent.
We can use ESCA on both conductive and insulating samples, which mean this technique
has a wide application for both organic and inorganic samples.
In Electron Spectroscopy for Chemical Analysis (ESCA), we use an X -ray beam to bombard
the surface of sample so we can measure the core electrons emitted. We have multiple types
of excitation sources: a non-monochromatic Al or Mg x-ray and a monochromatic Al x-ray
source. The choice of source is based on the sample under analysis and what information is
needed about the sample.We also perform “small spot ESCA”, which refers to the ability of
the electron analyzer to aperture down to an area as small as 75 microns in diameter. When
we combine this feature with a high-strength but small X-ray source, we are able to provide
a chemical analysis of features smaller than 100 microns in width.
02-03-01: DESCRIPTION OF ESCA SPECTROMETER
The ESCA spectrometer:
The principle of an ESCA spectrometer is shown i fig. VII.9. It comprises an X -ray tube as
a source, the source is in the upper left corner in the figure; the sample, which is in the
lower part of the figure; and a detector, that measures the electron flow. The detector
depicted in the figure determines the energy of the electrons by bending their path in a

magnetic field. The principle of an UPS spectrometer does not differ very much from that
of an XPS spectrometer, other than that the source is a UV lamp, of course.
In the UV photoelectron spectroscopy a suitable UV source is used. It is most often based

on the Helium I emission at 24.5874 eV or Helium II emission at 54.403 eV (2372.3 eller
5250.5 kJ/mol). In X-ray photoelectron spectrometer the source is an X -ray tube. The anode
material of the X-ray tube determines the wavelength of the emitted radiation. A few
examples are given in the table below.1 The principle of an X -ray tube is shown
schematically in fig. VII.

A magnesium anode emits X-ray radiation at 0.989 nm or 1253 eV. Its natural linewidth is
0.70 eV which is then the practical limit for the resolution of X-ray photoelectron
spectroscopy when using a non-monochromatised source. However, a suitable crystal can be
used as a monochromator in order to obtain the exactly correct wavelength. E.g., the Kα
band of aluminium at 0.83386 nm or 1486.7 eV can be monochromatised by using the quarz
surface 0101 to obtain a linewidth as low as 0.16 eV which is in practice the best resolution
that can be obtained with an ESCA spectrometer. The customary, not fully optimised,
adjustments in a spectrometer reduce the resolution so that the best performance one c an
expect in standard spectra is maybe 0.4 - 0.6 eV. In the case of non-monochromatised
radiation one can expect a resolution of 0.9 - 1.0 eV.
There are many types of electron detectors. The most common one is based on the same
principle as the ion detectors in the traditional mass spectrometers, i.e., the electrons move
in a strong electromagnetic field that bends their path the more the slower they propagate.
The field is adjusted so that the electrons with a given velocity hit the detector. The kinetic
energy can then be determined on basis of the strength of the electromagnetic field. Such a
hemispherical detector is shown schematically in fig. VII.11. Its resolution depends on the
electronic lenses that focus the electrons into the entrance slit of the detector, and of the
homogenity of the field in the detector. In most ESCA spectrometers the field in the
detector is kept constant and the the focusing lens system is adjusted so that the electrons
entering the detector have the correct energy. The altern ative method is to also adjust the
field in the detector. The latter type is often found in Auger spectronmeters because the
detector’s resolution increases and the influence of the low energy noise is reduced.
In modern spectrometers multi-channel detctors are used. In that case, the electromagnetic
field strength can be kept constant. One possibility is to use a CCD detector.
Other detector types are used rarely. In some cases a time -of-flight detector (ToF) may be
used. This type of detector is quite common for detection of ions, both in ordinary mass
spectroscopy and in SIMS but quite rarely used in detection of electrons.

The accuracy of the spectrometer’s scale for ionisation energies of the sample can be
verified by using known calibration samples. Some examples are given in the table
below.kända kalibreringsprov. 2 In the table are given the binding energies in electron volts
as measured by using two different X-ray sources at a resolution of 0.2 eV. The angle of
emission is set to 15◦ . The radiation from the aluminium soirce is monochromatised.
The sample is ionised and therefore the extracted electrons must be replaced in the sample.
Otherwise the sample soon gains a positive surface charge that makes further ionisation
difficult and causes a tilted background in the spectrum. For this reason the typical sample
material is metal.
Band positions in ESCA:
The observed electrons in the XPS originate from the core molecular orbitals that have to a
large extent retained their atomic orbital character. Therefore one can identify the elements
that the molecule comprises. X-ray photoelectron spectroscopy is a method for elemental
analysis. Tables over characteristic ionisation energies for the electron shells in various
atoms have been published. A summary is shown in the tables below.3 In this case, a Mg X -
ray source has been used. Because Auger bands are often observed in the ESCA spectra also
the chracteristic Auger band positions are reported here. Also they are highly characteristic
for the elements. The energies in bold face are those that one should locate first when
identifying the elements.
The binding energies in the tables below are for pure elements. The exact positions of the
bands depend to some extent on chemical shifts as illustrated in fig . VII.4. They give a hint
on the oxidation state of the atoms but no detailed conclusions of the chemical substances
can be drawn.

SOLVED PROBLEMS 01
108) Which of the following is a characteristic of ambient ionization techniques
Occurs in the vacuum of the mass spectrometer.
Direct analysis if the sample with little or no sample preparation.
Always uses a matrix to enhance sensitivity
Tends to exploit 'hard ionization' mechanisms
109) What are 'matrix effects' that are associated with electrospray ionization?
Matrix effects are the interference of other molecules in a sample on the number
of ions formed from an analyte.
The matrix effect leads to the formation of a Taylor cone during
electrospray ionization
The matrix effect relates to the coulombic repulsion in a solvent droplet as it
evaporates in an electric field

110) What is function of ion detector?
There are many types of electron detectors. The most common one is based on the
same principle as the ion detectors in the traditional mass spectrometers, i.e., the
electrons move in a strong electromagnetic field that bends their path the more the
slower they propagate. The field is adjusted so that the electrons with a given
velocity hit the detector.
111) What is the principle of the ESCA spectrometer?
The principle of an UPS spectrometer does not differ very much from that of an
XPS spectrometer, other than that the source is a UV lamp, of course. In the UV
photoelectron spectroscopy a suitable UV source is used. It is most often based on
the Helium I emission at 24.5874 eV or Helium II emission at 54.403 eV ( 2372.3
eller 5250.5 kJ/mol).
02-03-02: INTENSITIES OF ESCA

The intensities in ESCA:
The intensity of the spectral bands in ESCA depends on many factors. The most important
one is obviously the number of scattering centra, i.e., the concentration.
The inherent transition probability can be approximated on basis of the symmetry
properties. The transition moment obeys the equ
where Ψi is the wavefunction of the neutral, non-ionised atom or molecule describing an n-

electron system. The wavefunction Ψf describes the ionised system with n − 1 electrons and
ψe is the wavefunction of the departing electron. A symmetry analysis indic ates that the

departing electron’s wavefunction must have a suitable shape in order the transition
moment to be finite. The electron is observed at a very large distance from the positive
charge and therefore one can assume that the electron feels a centra l field. This allows the
use of atomic notations s and p for the shape of the wavefunction ψe. Therefore the terms s
or p channel are often used. The scattering theory leads to a similar conclusion.
The bands marked in bold face in the above tables are tho se that have the highest inherent
intensities.
Another important factor that affects the band intensity is the electron’s free path in the
material. The deeper the ionisation occurs the more difficult it is for the electron to reach
the surface of the sample and fly to the detector. The free path depends on the electron’s
kinetic energy. Therefore the intensity must be corrected for the electron’s energy, i.e., for
the energy of the X-ray source. If one uses radiation from an aluminium source (1487 eV)
the typical free path is 1.4 to 2.0 nm. This implies that overwhelmingly most of the
observed electrons originate from maximally 6 -8 nm below the sample surface.
More formally one can express the intensity of the incident X -ray radiation at the depth z in
the sample as
Most of the quantities are defined in fig. VII.12. The intensity I0 is the incident flow of X -
ray photons on the sample surface. Reflection R of the X -ray radiation can be ignored
provided that the angle θ is not very small, say under 5◦ . The quantity lhν is the free path
of the X-ray radiation in the material
The number of scattering centra, i.e., atoms in a unit volume is

The symbol n stands for the number of atoms per unit volume. This equation is valid if the
illuminated part on the sample surface is larger than the aperture of the de tector, A0. The
probability of photoelectric emission in the solid angle Ω is
where σ is the differential cross section of the photoemission and Ω is the angle between
the incident electron flow and the principal axis of the detector.
The probability that a photoelectron reaches the detector without collisions with atoms can
be calculated from the Lambert-Beer law as
Here le(E) stands for the electron’s free path between inelastic collisions in the material
when its kinetic energy is E. An electrons that experiences a collision looses energy and
contributes to the spectrum’s background instead of the characteristic spectral band of the
ionisation process.
The detector reading depends on the effectivity of the detector, D0, and on the fraction of
photoelectrons with the energy E that reach the analyser and are transported to the detector
at the energy E0, F(E0/E).
Summarising these contributions one can write the observed integrated intensity of
electrons from the sample surface to depth t as
When forming the ratio of integrated intensities for two substances A and B many of the
constants in the equations cancel. The ratio is
Based on these ratios it is possible to calculate the per cent ratios of the various
components n(A) on the surface, provided that the free paths le and the scattering cross
sectons σ are known. It is customary to compare the integrated areas of all bands of the
elements in the spectrum.
The accuracy obtained in quantitative analysis of most elements is in the range of per
milles. In optimal conditions one can reach an accuracy of a millionth part (ppm) but this
requires a very high concentration on the surface or an exceptionally long exposition time.

For the strongest spectral bands one may obtain relative atomic concentrations in porcent
that are 90 - 95 % of the true concentrations, but in normal samples typically 80 - 90 %. For
weak bands whose intensity is 10 - 20 % of the intensity of the strongest bands one can
expect a reliability of 60 - 80 %. The anslysis time varies between 1 and 10 min. Under
such standrad conditions one will be able to measure the concentrations in a
multicomponent system or determine the chemical shifts. The detection limit is 0.1 - 1.0 %
in number of atoms. Under optimal conditions one can reach a detec tion limit of 100 ppm
but this requires a measuring time of several hours (8 - 16 h).
The dimension of the analysis spot is typically 10 - 200 µm.
Examples of ESCA spectra:
In X-ray photoelectron spectroscopy one primarily measures the kinetic energy of th e
electrons. The spectrum is therefore often presented using this energy scale. However, the
quantity characteristic for the elements is the binding energy of electrons to the atom or
molecule. This quantity can be determined on the basis of the kinetic en ergy as
Before the spectrum can be analysed, the binding energy corresponding to each band must
be determined. Therefore the natural choise is to directly show the energies in the binding
energy scale. A spectrum of silicon in fig.VII.13. llustrates this .

The samples in XPS are most often metals or very thin surface coating, e.g., oxide.
Insulating materials are usually quite problematic as samples because there will be an
increasingly high positive surface charge the longer the experiment continues and this will
distort the background of the spectrum. Thin filmes can be placed on a metal substrate and
then one may in favorable conditions obtain a reasonably good spectrum of an insulating
material. The spectrum of polypropylene in fig. VII.14. is an exam ple of this.
The photoelectron spectum is sometimes shown in the original energy scale, i.e., as a
function of the kinetic energy. In this case the energy scale is inverted. The high
background will in that case be found at the low kinetic energies. The spectrum of gold is
shown as an example if this in fig. VII.15. One must of course know the wavelength of the
incident radiation and the work function of the sample in order to be able to identify the
bands whose position still depends on the binding energ y, of course.
The quantitative analysis is simplified appreciably if the variable background is removed
from the spectrum. However, it is not always obvious where the background line must be
drawn. Every manipulation of the spectrum must be made carefully and be documented in
detail. Fig. VII.16. Show an example of manipulating the spectrum.
The most common satellite structures observed in the spectrum are plasmon structures. An
example is shown in fig. VII.17.

SOLVED PROBLEMS 02
112) Which of the following classifies Chemical Ionization most accurately
A hard ionization technique
A soft ionization technique
neither hard or soft ionization
A desorption ionization technique

113) Which one of the following element is used in cryoscopy to obtain very low
temperature
A) C
(B) Li
(C) B
(D) He
114) What is the intensity of ESCA?
The intensity of the spectral bands in ESCA depends on many factors. The most
important one is obviously the number of scattering centra, i.e., the
concentration.The inherent transition probabili ty can be approximated on basis of
the symmetry properties.
115) What is ESCA Spectra?
In X-ray photoelectron spectroscopy one primarily measures the kinetic energy of
the electrons. The spectrum is therefore often presented using this energy scale.
However, the quantity characteristic for the elements is the binding energy of
electrons to the atom or molecule.
02-03-03: SPECTROMETER
An apparatus for recording and measuring spectra, particularly as an approach of analysis.
A spectrometer is a scientific tool used to split light into an array of various colors, called a
spectrum.
The capacity of spectroscopy to determine chemical make -up drove its innovation as well
as continues to be one of its main uses. Spectrometers are utilized in astronomy to evaluate
the chemical structure of stars, planets and collect information on the origin of space.
Spectroscope
A spectroscope is a device that measures the spectrum of light. Early variations had a slit, a
prism, as well as a display with markings to show different wave lengths or frequencies.
Spectrograph
A spectrograph is an instrument that separates incoming light by its wavelength or
frequency and documents the resulting spectrum in some sort of multichannel detector, like
a photographic plate.
Lots of astronomical observations use telescopes as, essentially, spectrographs.
Components of Spectrometer:
1. Source of light
The role of the light source is to emit a continuous spectrum at a specific wavelength. The
tungsten light is usually used in the visible range of 6 ~ 12V. In the near-ultraviolet area, a
hydrogen lamp or deuterium lamp is used as the source of light.
2. Monochromator
The monochromator is the decomposition of the continuous spectrum given off by the
source of light for monochromatic light, it is the core component of the spectrometer.

The dispersion capability of the monochromator is more powerful, the greater the
resolution, the pure monochromatic light. The typical dispersion elements are prisms and
gratings
3. Collimator
It consists of a fixed metal tube with a convex lens at one end and an adjustable slit at the
other end. When the slit is at the focus of the convex lens, the rays of light coming out
become parallel.
4. Detector
The function of the detector is to accept the transmitted light from the c uvette as well as
transform it into electrical signals for measurement.
When measuring absorbance, it is measured by transforming the strength of light into an
electrical current. This photoelectric converter is called a photoelectric detector.
5. Signal Display System

The feature of a signal display system is to present or record an enhanced signal in the form
of absorbance, A, or transmittance T. A basic spectrophotometric meter display device is
frequently used galvanometer, microammeters, digital screen recorder.
Working of Spectrometer
One of the most standard layouts of a modern spectrometer is a set up of a slitted
display, a diffraction grating, and a photodetector. The display allows a beam into the
interior of the spectrometer, where the light goes through the diffraction grating.
The grating separates the light into a beam of its component colors, similar to a prism.
Spectrometers have a collimator that makes the light waves parallel and coherent,
therefore making them a lot more focused.
This uses especially to spectrometers made use of in telescopes. The light after that
shows onto a detector that gets specific wavelengths.
Uses of Spectrometer
 A spectrometer is a tool for determining wavelengths of light over a wide variety of
electromagnetic spectrum.

 It is commonly utilized for spectroscopic analysis of sample materials.
 The incident light from the light source can be transmitted, soaked up, or mirrored
through the sample.
 The changes that occur throughout the interaction of incident light wit h the sample
show the features and characteristics of samples .
SOLVED PROBLEMS
116) In hollow cathode lamp of atomic absorption spectroscopy, the cathode is made up of /
coated with _______
(A) Graphene
(B) Multi walled carbon nanotube
(C) Carbon black
(D) same as analyte element of interest
117) saq

118) What is Spectrophotometer used for?
A spectrophotometer is an analytical instrument used for the objective
calculation of visible light, UV light, or infrared light emission or reflection.
Spectrophotometers measure intensity as a function of the wavelength of the
light source.
119) What is the difference between spectrometer and A spectrophotometer?

A spectrometer is an aspect of the most responsible spectrophotometer for the
calculation of different objects. A spectrophotometer is a comprehensive
device that involves a light source, a way of collecting the light that has
interacted with the objects being measured, and a measurement spectrometer
02-03-04: XPS/ESCA
XPS/ESCA
X-ray photoelectron spectroscopy (XPS), also known as electron spectroscopy for
chemical analysis (ESCA), is a surface chemical analysis technology, which is mainly
used to characterize the surface elements and their chemical states of materials. It is an
analytical technique with a sampling range from surface to depth of about 50-70Å. It
can perform chemical state analysis, depth analysis, and analyze the chemical linkages
of various elements on the surface of the material, and it is not limited by the
conductivity of the sample

PRINCIPLE
XPS is a spectroscopic method that uses high-energy photons in the X-ray range to
irradiate the measured samples and measure the photoelectron energy distribution
caused by this. Under the action of X-ray, all kinds of orbital electrons may be excited
into photoelectrons from atoms. Because the binding energy of various atomic and
molecular orbital electrons is certain, it can be used to determine the electronic
structure of solid surface and the chemical composition of surface components. In the
latter application, it is generally called electron spectroscopy for chemical analysis
(ESCA).
STRENGTHS
 The surface of the sample is less damaged by radiation.
 It can detect all the elements in the periodic table except H and He, and has high absolute
sensitivity.
 Quantitative analysis, including chemical state differences between samples.
 Suitable for a variety of materials, including insulation samples (such as paper, plastic
and glass).
 Oxide thickness measurement.
 Surface analysis and research can be carried out under low vacuum, which can not be
done by other methods.
IDEAL USES
 Structural analysis
 Organic structure analysis.
 Surface analysis.

 Analysis of biological macromolecular structure.
 Analysis of polymer structure.
 Catalyst surface analysis.
 Structure analysis of environmental pollutants.
 Qualitative analysis
 Identification methods of element composition and chemical state.
 Identification of accompanying peak.

Mixture analysis.
APPLICATIONS & INDUSTRIES
Use this technology to help customers research and develop and develop processes in a
variety of applications in different fields.
 Measure surface composition and chemical state information.
 Describe the cleaning process.
 Analyze the main components of powder and chips.
 Surface analysis of organic materials, inorganic materials, stains, and residues, identify pollution
sources.
 Identify and quantify functional testing of polymers before and after surface changes.
 Measure the thickness of the lubricant on the hard drive.
 Obtain thin film (conductive and non-conductive) depth profiles for the horizontal elements of the
material body.
 Thin film oxide thickness measurement, such as SiO2, Al2O3, etc., or estimate the difference in
oxide layer thickness between two samples.
 The detection limit is usually ~ 0.01% and the smallest analysis area is ~10 µm.
SOLVED PROBLEMS 04
120) In ESCA process, the photon ejects which of the following?

a) 1s electron
b) 1p electron
c) 2s electron
d) 2p electron
121) Electron ionisation can produce ESCA electrons.

a) True
b) False

122) What is difference between spectroscope and spectrograph?
A spectroscope is a device that measures the spectrum of light. Early variations had a slit, a
prism, as well as a display with markings to show different wavelengths or frequ encies . A
spectrograph is an instrument that separates incoming light by its wavelength or frequency
and documents the resulting spectrum in some sort of multichannel detector, like a
photographic plate.
123) What is siganal Display System?
The feature of a signal display system is to present or record an enhanced signal
in the form of absorbance, A, or transmittance T. A basic spectrophotometric
meter display device is frequently used galvanometer, microammeters, digital
screen recorder.
CHECK POINT
1) ESCA focuses on which of the following information?
(a) Mass of the electron
(b) Charge of the electron
c) Binding energy of the electron
(d) Mass of atoms
2) Qualitative chemical analysis is very often performed using which of the following?
(a) ESCA
(b) SIMS
(c) AES
(d) Ion spectroscopy
SUMMARY
The corresponding shifts in core-electron spectroscopy were detected and interpreted 40
years later. Quantitative evaluation of the core-electron binding energies and shifts became
possible when sufficiently powerful computers were available in the 1960’s. During the past
four decades a large number of more or less sophisticated computational methods have been
developed, and it is now possible to evaluate the binding energies – including vibration
levels and the satellite structure – and chemical shifts with an accuracy of the order of 0.1
eV, also for relatively complex molecules.
KEY WORDS
Inelastic scattering,Hard Segment, Survey spectrum,High resolution Sectrum,

REFERENCES
1] M. Siegbahn, Spektroskopie der Röntgenstrahlen (Springer, Berlin, 1931).
[2] A. Lindh, Z. Phys. 6, 303 (1921)
[3] J. Bergengren, Z. Phys. 3, 247 (1920).

1) C
2) A
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=UMR7vel76JI
https://www.youtube.com/watch?v=Oz-bQk5jxvk
WIKIPEDIA
https://www.sciencedirect.com/topics/engineering/electron-spectroscopy-for-chemical-
analysis
https://www.nanolabtechnologies.com/instrument -xps-esca/
OER
____
REFERENCE BOOKS
2001.
3. C.Duval, Inorganic Thermogravimetric Analysis, Elsevier Amsterdam, 1962.
1965.

CREDIT 02-UNIT 04: AUGER ELECTRON SPECTROSCOPY
LEARNING OBJECTIVES
 Explain the concept of Auger electron Spectroscopy spectroscopy
 Predict the number of fundamental modes of vibration of a molecule
 Explain the working of schematics of AES
INTRODUCTION
The Auger Effect is named after its discoverer, Pierre Auger, who observed a tertiary effect
while studying photoemission processes in the 1920s. Auger electrons are emitted at
discrete energies that allow the atom of origin to be identified. The idea of using electron -
stimulated Auger signals for surface analysis was first suggested in 1953 by J. J. Lander.
The technique became practical for surface analysis after Larry Harris in 1967
demonstrated the use of differentiation to enhance the Auger signals.
Today Auger electron spectroscopy is a powerful surface analytical tool to probe surfaces,
thin films, and interfaces. This utility arises from the combination of surface specificity
(0.5 to 10 nm), good spatial surface resolution (as good as 10 nm), periodic table coverage
(except hydrogen and helium), and reasonable sensitivity (100 ppm for most elements).
02-04-01: PRINCIPLE OF AUGER ELECTRON SPECTROSCOPY

Principle of AES:
•A fine focused electron beam bombards the sample and ejects an electron of the inner shell
of the atom.
• This vacancy must be refilled by an electron from a higher energy level.
• When the higher energy electron fills the hole, the release of energy is transferred to an
electron in an outer orbit electron.
• That electron has sufficient energy to overcome the binding energy and the work function
to be ejected with a characteristic kinetic energy.
•The ejected electron is referred to as an Auger electron after Pierre Auger. • The Auger
process require three electrons, thus we can not detect H and He but can dete ct all other
elements from Li on up.

Figure 2 depicts the schematics of Auger phenomenon is solids. The figure shows KL2L3
Auger transition which involves ionization, relaxation, and emission, and is summarized
below:
a. Ionization: Highly energetic incident electrons remove an electron from the core shell of
the atom, leading to the formation of a vacancy in K -shell. Thus, an electronically excited
ion is produced
b. Relaxation: The K-shell vacancy created during previous step is quickly filled by an
electron coming from L2 shell via non radiative transition.
c. Emission: An electron (Auger electron) is emitted from L3 shell, thereby releasing the
extra energy of the excited ion.
Auger transitions are named on the basis of the energy levels involved in the process, e.g.,
the transitions involved in the above figure is named KL2L3.
In certain cases, such as atoms having high atomic numbers, many Auger transitions are
available. However, most of them have low probability of occurring. Further, some of the

energetically allowed transitions are also forbidden by the selection rules. If a valence
electron takes part in the Auger transition, letter V is used (such as KLV, KVV, etc.).
Transitions involving core level electrons use letter C (such as CVV). Transit ions of ABB
(such as KLL, LMM) type are strongest. Another strong transitions are AAB type (also
called as Coster-Kronig) transitions. Emission of X-rays is a competing phenomenon for
Auger process since the energy difference between the core and outer lev els can equally be
released in the form of a characteristic X-ray. Therefore, the sum of the yields of Auger
emission and X-ray emission is one. AES typically operates in the energy range where the
probabilities of Auger emission are much higher than that for X-ray emission. In addition to
this, the cross-section for Auger transitions in elements having lo w atomic numbers is much
higher.
Kinetic Energies of Auger Electrons:
AES includes measuring the K.E. of Auger electrons which are characteristic to the
elements of the sample. Uncertainties of upto 1 -2 eV are to lerable in measurement of
K.E.for elemental identification. However, for analysing Auger chemical shifts, this
uncertainty in K.E. should not exceed 0.1-0.2 eV. Nowadays, databases are available which
can be compared with the obtained results, however, earlier AES relied on measuring the
K.E. of electrons. The steps involved can be summarized as follows:
K.E. of an Auger electron is expressed as the difference in energies of singly ionized initial
state and doubly ionized final state. Since first principles calculations of this energy is
highly complex, uncertainties upto ~10eV are acceptable in most situations, several
approximations are to be made in order to determine the K.E. of Auger electrons. Suppose
in a hypothetical ABC type Auger transition, a vacancy is created in A level by removing an
electron from it; this vacancy getsfilled by an electron from
B level; and Auger electron is emitted from C level. Let the B.E. of electrons in neutral
atom for A, B, and C levels are EA, EB, and EC respectively. When electron from B
occupies vacancy in A level, an energy (EA -EB) is transferred to the third (C level)
electron, which is the Auger electron. Thus, the K.E. (EABC) of Auger electron can be
expressed as:
𝐸𝐴𝐵𝐶 ≈ 𝐸𝐴 − 𝐸𝐵 – 𝐸c (1)
From Eq. (1), it is evident that the K.E. of Auger electron does not depend on the energy of
the incident beam, rather it only depends upon the energy levels of the atoms present in the
sample. Thus, the K.E. of Auger electrons represent the elemental composition at thesurface
of the sample. Each element shows distinct set of Auger peaks corresponding to its unique
set of energy levels. For instance,the energy for KL1L3Auger transition i n aluminiumcan be
calculated as:
𝐸𝐾𝐿1𝐿3 ≈ 𝐸𝐾 − 𝐸𝐿1 − 𝐸𝐿3

1560 – 118 – 73
1369eV
The measured value of this energy is 1354 eV. Two corrections can be considered to avoid
the large disparity. Eq. (1) needs to be alteredto includework function of spectrometer
because Auger energies are usually referenced to the Fermi level. If good electrical contact
exists between the sampleand sample holder, then the Fermi levels of the sample and
instrument are equal. Therefore, the K.E. of ABC Auger electron is approximately given as:
𝐸𝐴𝐵𝐶 ≈ 𝐸𝐴 − 𝐸𝐵 − 𝐸𝐶 – 𝜙c (2)
Arepresents the work function of spectrometer, and its typical value is ~ 4 eV, 𝐸𝐴𝐵𝐶 come
out to behere, 1365 eV as the energy of KL1L3Auger transition in aluminium. This
reduces the disparity in measured and calculated values to 11 eV. For a neutral atom, Eq.
(1) can be further filtered by considering the change in B.E. of a level accompanyingion
formation:
here, 𝐸𝐶∗ represents the B.E. of a level in the presence of a core hole. Eq. (3) ca n be
employed to determine energy of Auger electrons based on various empirical
approximations.
SOLVED PROBLEMS 01
124) The characterisation of auger spectroscopy can be achieved up to which of the
following depths?
a)1 nm
b) 2 nm
c) 4 nm
d) 8 nm
125) Auger electron spectroscopy can be used for surface chemical analysis in a way
similar to which of the following?
a)ESCA
b) SIMS
c) ISS
d) Ion spectroscopy
126) What is Principle of AES?
•A fine focused electron beam bombards the sample and ejects a n electron of the
inner shell of the atom.
• This vacancy must be refilled by an electron from a higher energy level.
• When the higher energy electron fills the hole, the release of energy is
transferred to an electron in an outer orbit electron.
127) Discus the kinetic energies of Auger Electron.

AES includes measuring the K.E. of Auger electrons which are characteristic to
the elements of the sample. Uncertainties of upto 1 -2 eV are to lerable in
measurement of K.E.for elemental identification.
02-04-02: AES
Instrumentation:
Surface sensitivity in AES technique (Figure 3) evolves from the fact that in solid
materials, emitted electrons generally possess energies in the range of 50 eV - 3 keV and
relatively shorter mean free path. Therefore, escape depth of ele ctrons is limited to few nm
in the target surface which gives AES a high surface sensitivity. Due to lower energy of
Auger electrons, typical AES runs under the condition of ultra -high vacuum. This prevents
electron scattering from residual gas atoms and d evelopment of a thin "gas (adsorbate)
layer" on the sample surface which results in degradation of the analytical performance.
A standard AES setup (Figure 3) involves the following components: (a) electron source
and electron optical column forming an electron probe on the sample surface; (b) ion
optical column to clean the surface and sputtering for depth profiling; (c) electron energy
analyser; (d) a secondary electron detector and a pulse counter; and (e) computer control
and display systems. Modules (a-d) are located insidean ultra high vacuum chamber.
a. Electron Optical Column:An optical column focuses the electron beam (from an electron
source) to the sample surface. The electron beam must be monoenergetic, of small size, and
highly bright. Electrons irradiating the sample have energy in 2 -10 keV range with a beam
current of 10-8 to 10-5A.Scanning Auger microscopy uses energy upto 35 keV and current
10-9A to create a beam of ~100 Å diameter. The electron source must haveprolonged life
and higher temporal stability. Four major types of electron source are: (i) Tungsten
thermionic emitter with ~2700 K operation temperature. They produce low current density.
Owing to low brightness and large beam sizes, they are preferred for AES analysis where

high lateral resolutions are required. (ii) The lanthanum hexaboride (LaB6) thermionic
emitter with operating temperature of ~1850 K and lower work function than tungsten, can
provide high lateral resolutions since they generate high current densities. (iii) Tungs ten
single crystal based cold field emitter, working at room temperature in the presence of a
high electrostatic field and creates high brightness. However, this emitter becomes unstable
on encountering residual gases and thus ultra low pressures (10 -10torr) are needed. (iv) Hot
field or ZrO2/W Schottky-type field emitter, operable at ~1800 K. This type of emitter can
produce high current density.
b. Ion Optical Column: Ion source of electron impact type are used in AES equipments for
depth profiling and sputter cleaning purposes. Heated filament generates electrons which
are then accelerated by cylindrical grid such that they haveenough energy to ionize gas
atoms uponcollision. The ions thus produced are accelerated into a focusing lens column.
Typically, inert gases (e.g., Ar and Xe) are used with a hot tungsten filament.
c. Electron Energy Analyzers:The number of electrons emitted (N) are measured as a
function of their energy (E) by using electron energy analyzers. Most widely employed
analyzers are:(i) RFA or retarding field analyser. (ii) CMA or the cylindrical mirror
analyser. (iii) CHA or concentric hemispherical analyser. Retarding field analyzers suffer
from inadequate energy resolution and poor signal -to-noise ratios due to average
transmission efficiency. Thus, RFA is generally employed in low energy electron diffraction
investigations, and not preferred for AES. CMA has high transmission efficiencies, compact
size and is simple to use, making them suitable for AES. CHA is used for AES whenever
chemical state analysis is performed since they have high resolutions. CHAs include an
input lens and hemispherical analyser, and are a commonplace in XPS energy analyzers.
CMA and CHA are band pass filters (BPF) while RFA is high pass filter. The BPF allows
passage of electrons within a band of energy (E) at a pass energy (E), leading tothe energy
resolution of E/E.As RFA detects electrons having energy greater than a specific energy, E,
the spectrum is differentiated once to determine N(E) spectrum.
d. Electron Detector: After exiting the analyser, the electrons reach the detector which
amplifies and counts them using an electron multiplier (channeltron or microchannel plate,
MCP). The interior of channeltron (cone-shaped dynode) is coated, such that when one
electron strikes it, many secondary electrons are generated. These secondary electrons are
then accelerated to the anode. Several intervening collisions cause an avalanche effect,
leading to a gain of ~108 for a channeltron. MCP comprises several small cha nneltons
joined together to create a disc. Electron intensity is measured via pulse counting.
e. Computer and Display System:Sophisticated computer control, data processing, and
display systems are common to all modern AES instruments. The functions of com puter
control system are: (i) setting up conditions for analysis; (ii) efficient collection and storage
of data; (iii) data processing; and (iv) displaying results in the form of spectra.

In this experimental configuration (Figure 3), first the focused ele ctrons get incident on a
solid sample and then the emitted electrons gets deflected towards a cylindrical mirror
analyzer. In detector, an Auger electron gets multiplied and signal is advanced for data
processing. Finally, the accumulated Auger electrons a re recorded as a function of energy
against broad secondary electron background spectrum. Because the Auger peaks have
small intensities relative to the background noise, AES is generally operated in derivative
mode that highlights Auger peaks by modulating the electron collection current by applying
small AC voltage. Using setup shown in Figure 3, by detecting the signal at frequency ‘ω’
and plotting one can get the Auger fine structure. In this Auger electron structure, one can
clearly see the little secondary peaks neighbouring the main Auger peak. The secondary
peaks arise because an element may be present on the surface in different chemical states.
Data Recording, Processing, and Output System:
•The Auger electrons appear as peaks on a smooth backgroun d of secondary electrons.
• The background is usually sloping therefore, the Auger spectra are usually recorded in a
differential form.
• In the differential mode it is easy to increase the system gain to reveal detailed structure
not directly visible in the undifferentiated spectrum.
• At present, the data in commercial instruments are acquired digitally and can be presented
in either analog or digital mode.
• A conventional Auger electron spectrometer uses a lock -in amplifier.
• The oscillator in this amplifier superimposes a sinusoidal modulation on the potential
applied to the outer cylinder of the analyzer.
• The AC component of the signal is decoupled from the multiplier high voltage and
detected in the lockin amplifier.
• The output is then fed to an x–y recorder.
•The amplitude of the modulation is chosen to yield a compromise between sensitivity and
resolution.
• A typical modern Auger electron spectrometer collects the data in the N(E) versus E
integral mode.
• The data are then mathematically differentiated using computer software to yield Auger
spectra.
Advantages:
• Surface sensitive. • Elemental and chemical composition analysis by comparison with
standard samples of known composition. • Detection of elements heavier than Li. Very good
sensitivity for light elements. • Depth profiling analysis: quantitative compositional
information as a function of depth below the surface. • Spatial distribution of the elements
(SAM): Elemental or even chemical Auger maps analysis in lines, points and areas.

SOLVED PROBLEMS 02
128) AES is limited when it comes to very high resolution studies.
a) True
b) False
129) Qualitative chemical analysis is very often performed using which of the
following?
a) ESCA
b) SIMS
c) AES
d) Ion spectroscopy
130) What are genral uses of AES?
General Uses • Surface composition analysis for metals, powders, insulators. •
Identification of particulates, localized dopants or contaminants, visual defects. •
Investigation of submicrometer dimension structures. • Grain boundary
investigations, e.g. intergranular corrosion. • Analysis of surface coatings and thin
films. • When combined with ion sputtering, elemental depth profiling of surface
and/or interfacial layers.
131) What is Process of AES?
The Auger process: Emission of an initial electron leads to the emission of a
characteristic (Auger) electron. It is a surface specific technique utilizing the
emission of low energy electrons in the Auger process and is one of the most
commonly employed surface analytical techniques for determini ng the
composition of the surface layers of a sample.
132) What kinds of problems are best tackled by AES?

133) How do you calculate the energy of an Auger electron.?
02-04-03: UPS
Ultraviolet Photoelectron Spectroscopy - UPS In early UPS, the sample was a gas or a
vapor that is irradiated with a narrow beam of UV radiation. More modern UPS instruments
are now capable of studying solids as well. The photoelectrons produced are passed through
a slit into a vacuum region where they are then deflected by magnetic or el ectrostatic fields
to give an energy spectrum. UPS is sensitive to the very near surface region, up to around
10 nm in depth.

There are two main areas UPS is used to study:
1. Electronic structure of solids.
2. Adsorbed molecules on metals.
Specific examples of UPS studies include:
1. The measurement of molecular orbital energies that can be compared to theortical
values calculated from quantum
2. Determination and assignment of bonding, nonbonding, antibonding molecular
orbitals.
3. The binding and orientation of adsorbed species on the surface of solids.
Spectral output:
Briefly, the spectrum produced from a UPS experiment has peaks that correspond to the
ionization potentials of the molecule. These also correspond to the orbital energies. Because
of this, UPS can also give information on the vibrational energy levels of the ions formed.
Limitations:
UPS is capable only of ionizing valence electrons, which limits the range and depth of UPS
surface experiments. Conventional UPS has relatively poor resolution.
Advantages:
Ultraviolet radiation has a very narrow line width and a high flux of photons available from
simple discharge sources. Higher resolution UPS scans allow for the observation of the fine
structures that are due to vibrational levels of the molecular i on which, then, allows
molecular orbital assignment of specific peaks.
APPLICATION:
The UPS measures experimental molecular orbital energies for comparison with theoretical
values from quantum chemistry, which was also extensively developed in the 1960s. The
photoelectron spectrum of a molecule contains a series of peaks each corresponding to one
valence-region molecular orbital energy level. Also, the high resolution allowed the
observation of fine structure due to vibrational levels of the molecular ion, which facilitates
the assignment of peaks to bonding, nonbonding or antibonding molecular orbitals.
The method was later extended to the study of solid surfaces where it is usually described
as photoemission spectroscopy (PES). It is particularly sensitive to the surface region (to
10 nm depth), due to the short range of the emitted photoelectrons (compared to X-rays). It
is therefore used to study adsorbed species and their binding to the surface, as well as their
orientation on the surface.
A useful result from characterization of solids by UPS is the determination of the work
function of the material. An example of this determination is given by Park et al.Briefly, the
full width of the photoelectron spectrum (from the highest kinetic energy/lowest bindi ng
energy point to the low kinetic energy cutoff) is measured and subtracted from the photon
energy of the exciting radiation, and the difference is the work function. Often, the sample
is electrically biased negative to separate the low energy cutoff from the spectrometer
response.

SOLVED PROBLEMS 03
134) Electron ionization can produce which of the following?
a) ESCA electron
b) Auger electron
c) Ion
d) Photon
135) Electron ionisation can produce ESCA electrons
a) True
b) False
136) How does produce Auger Electron?
Two Ways to Produce Auger Electrons 1. The X-Ray source can irradiate and
remove the e - from the core level causing the eto leave the atom 2. A higher level
e- will occupy the vacancy. 3. The energy released is given to a third higher level
e- . 4. This is the Auger electron that leaves the atom. The axial e - gun can
irradiate and remove the core e - by collision. Once the core vacancy is created,
the Auger electron process occurs the same way.
137) What is probability of Auger emission?
The Probability of Auger Emission • AES usually performed using electron source
not x-rays (experimentally simpler and cheaper). • Basic steps in Auger electron
creation: (1) Creation of core hole. (2) Creation of Auger electron by relaxation. •
For maximum sensitivity of KLL Auger electron with KE 1000 eV, set incident
beam energy to ~ 3000 eV
138) Explain the differences between AES and EDS.
139) How is depth profiling performed?
02-04-04: CHEMICAL ANALYSIS BY AES

A) Qualitative Chemical Analysis by AES:
Auger electron spectroscopy finds applications mostly for the qualitative and quantitative
analyses of surface composition. A lesser, but equally important, application is for the
determination of the oxidation states of surface atoms from changes of Auger peak shap es
and from the shifts of Auger emission energies from inner shell excitations.
With the exception of hydrogen and helium, all other elements are detectable by AES.
Using this technique, surface segregation of various impurities has been found commonly
on most surfaces, Carbon, sulfur, calcium, and oxygen are the most common impurities that
segregate at the surface and their removal is essential in many cases. It shows the Auger
spectra of dirty and cleaned Au-Ag alloy surfaces. Chemical cleaning and ion bombardment
are used most frequently to remove unwanted impurities from the surface. It should be
remembered that the bulk of the specimen can be a continuous supplier of impurities to the
surface. Therefore, most cleaning treatments only reduce the impurity concentration in the
near surface region. Heat treatment of the samples can replenish the surface impurities by
diffusion from the bulk. Conversely, heating can dissolve surface impurities in the bulk on
account of the increased solubilities at higher temp eratures. The qualitative surface
chemical analysis by AES has opened up many fields of surface science to definitive

studies, including heterogeneous catalysis and corrosion. At present almost every
fundamental surface study includes Auger or photoelectro n spectroscopy analysis of the
surface composition as an integral part of the investigation.
B) Quantitative Chemical Analysis by AES:
By suitable analysis of the experimental data, as well as by the use of suitable reference
surfaces, the Auger electron spectroscopy can provide quantitative chemical analysis in
addition to elemental composition analysis of the surface. It is possible to separate the
surface composition from the composition of layers below the surface by appropriate
analysis of the Auger spectral intensities. In this way the surface composition as well as the
composition in the near surface region can be obtained.
The Auger peak intensity ratios can be calculated by properly taking into account the
attenuation of the emitted Auger electrons by the atomic layers above. By comparing the
calculated intensities with those obtained by experimeuts, quantitative chemical analysis
can be performed. Since both the adsorbate and the substrate Auger peak intensities vary as
the surface coverage changes, there is enough experimental information in most cases to
detect when monolayer coverage is reached and thus calibrate the amount adsorbed.
A simple technique to utilize the Auger spectrum to determine will also be the coverages
and growth mechanisms of deposits will also be / described below. This method consists of
plotting the Auger peak-to-peak signal intensity from the substrate against the similar
signal from the adsorbate. This technique enables one to study the growth of deposits of
any adsorbate-substrate system. We apply this method to the calibration of coverage of
carbon and oxygen “deposited on platinum.
C) Analysis of Auger Intensities:
Auger has principally been used as a means of performing qualitative analysis of surfaces
that is to identify or verify the presence of various atomic species. For this purpose AES is
certainly the best of all available techniques. Also of interest is the use of AES as a means
of quantitatively analyzing a surface to determine how much of an impurity or alloyi ng
component is present. This endeavor has occupied the time and efforts of a growing number
of workers in the last eight years a~.d it has been successful.
SOLVED PROBLEMS 04
140) Which of the following is an Auger transition starting from a hole in 1s levels which
would be filled up from the 2p level?
a) KLM transition
b) KLL transition
c) LMN transition
d) LLM transition
141) In Auger process, an electron drops to fill which of the following?

a) 1s hole
b) 1p hole
c) 2s hole
d) 2p hole
142) What is advantage and disadvantage of AES?
Advantages • Surface Sensitive • Elemental and Chemical composition and
analysis by comparing sample to known samples. • Quantitative composition
information as a function of depth below the surface • Good for spatia l
distribution of elements in sample (structure). • Disadvantages • Samples must be
able to compatible with ultra high vacuum • Samples must be conductive •
Possibility of beam damage for organic molecules • Cannot detect hydrogen or
helium • Quantitative detection is dependent on the element, but accurate to high
sensitivity
143) What is Data Analysis of AES?
Data analysis is a technique that may be helpful in interpreting multidimensional
data sets with overlapping spectral features. They are generated: • Eith er in
chemical analysis problems where the same spectral region is studied on different
samples (e.g. metal oxide, hydroxide, sulphide, • Or either in depth profiling
studies where the same sample is measured under different conditions (e.g., a
paint layer on top of a substrate). • The two most commonly applied multivariate
techniques are LLSF (linear least squares fitting) and FA (factor analysis). • Both
assume that each spectrum can be represented by a linear combination of
component spectra
144) How are Auger electrons produced?
145) Why is AES surface sensitive?
CHECK POINT 02-04
1) Auger electron spectroscopy involves the irradiation of the surface to be
analysed with a beam of electrons of energy in the _________ range.
2) Which of the following is the detection limit of Auger Electron
Spectroscopy?
a) 0.1% monolayer
b) 0.5% monolayer
c) 1% monolayer
d) 2% monolayer
3) Which of the following denotes the sample destruction that occurs in
Auger electron spectroscopy?
a) None in 95% of sample
b) None in 99% of sample
c) None in 100% of sample
d) Frequent
4) How is the specificity of Auger electron spectroscopy?
a) Very bad
b) Bad
c) Good
d) Very good
SUMMARY
 AES uses a focused e-beam to excite Auger electrons

 Auger electrons have energies characteristic of the elements
 Auger electrons - reveal the elemental composition and the chemistry of the surfaces
 Chemical bonding of the atoms
 Depth profiling in conjunction with ion sputtering
 High spatial resolution of the electron beam and surface specificity allows for high
resolution microanalysis
 AES attributes: high lateral resolution, reasonable sensitivity (100 ppm), semi -
quantitative analysis without empirical standards, and chemical bonding
information.
KEY WORDS
Auger Electron, Auger electron spectroscopy,Auger spectrum ,Auger peak,Auger Trasition.
REFERENCES
1. Thomas A., Carlson (1975). Photoelectron and Auger Spectroscopy. New York: Plenum Press. IS
BN 0-306-33901-3.
2. Briggs, David; Martin P. Seah (1983). Practical Surface Analysis by Auger and X-ray Photoelectr
on Spectroscopy. Chichester: John Wiley & Sons. ISBN 0-471-26279-X.
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=jKd4VgHh_2M
https://www.youtube.com/watch?v=L8uRxPqpqn8
WIKIPEDIA
https://en.wikipedia.org/wiki/Auger_electron_spectroscopy
https://serc.carleton.edu/msu_nanotech/methods/a es.html
OER
____
REFERENCE BOOKS
1. H. Bubert, J. Rividre, and W. Werner (201 I ) Auger Electron Spectroscopy, in Surface
and Thin Film Analysis: A Compendium of Principles, Instrumentation, and
Applications, Second Edition (eds G. Friedbacher and H. Bubert) , Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim, Germany.
2. S.N. Rarnan, D.F. Paul, J.S. Hamrnond, and K.D. Bomben, Microscopy Today, 2011, 19,
12-15.
3. S. Tougaard (2009) Quantification ofSurface and Near -Surface Cornposition by AES
and XPS, in Handbook of Surface and Interface Analysis Methods for Problem-Solving,
Second Edition (eds J. Rividre and S. Myka), CRC Press, Boca Raton, Florida

IV. Young and G. Hoflund (2009) Photoelectron Spectroscopy (XPS and UPS),
Auger Electron Spectroscopy (AE), and lon Scattering Sp ectroscopy (ISS), in
Handbook of Surface and Interface Analysis Methods for Problem -Solving,
Second Edition (eds J. Rividre and S. Myhra), CRC Press, Boca Raton, Florida.
4. N. Tumer (1997) X-ray Photoelectron Spectroscopy and Auger Electron Spectroscopy,
in Analyical Instrumentation Handbook, Second Edition (ed G. Ewing), Marcel Dekker,
Inc, New York, New York.
5. H. Liith (2010) Auger Electron Spectroscopy, in Solid Surfaces, Interfaces and Thin
Films, Fifthe Edition, Springer, New York, New York.

C REDIT 03

CREDIT 03-UNIT 01: DIFFRACTION METHODS
LEARNING OBJECTIVES
 State diffraction and need of diffraction in crystallography
 Compare optical and X-ray diffraction
 Out line the factors which are important in diffraction.
 Explain the processes of X-ray emission and the basic outline of an X -ray tube
INTRODUCTION
Introduction. Much of our understanding of the properties of polycrystalli ne materials has

been gained by studies of isolated single crystals, since such studies permit measurement of
the properties of the individual building blocks in the composite mass. Because single
crystals are usually anisotropic, research of this kind alw ays requires accurate knowledge of
the orientation of the single crystal test specimen in order that measurements may be made
along known crystallographic directions or planes. By varying the crystal orientation, we
can obtain data on the property measured (e.g., yield strength, electrical resistivity,
corrosion rate) as a function of crystal orientation.
In this chapter the three main x-ray methods of determining crystal orientation will be
described: the back-reflection Laue method, the transmission Laue method, and the
diffractometer method. It is also convenient to treat here the question of crystal deformation
and the measurement of this deformation by x -ray methods. Finally, the subject of relative
crystal orientation is discussed, and methods are give n for determining the relative
orientation of two naturally associated crystals, such as the two parts of a twin or a
precipitated crystal and its parent phase.
03-01-01: SINGLE CRYSTAL X RAY DIFFRACTION
The back-reflection Laue method: As mentioned in Sec. 3-6, the Laue pattern of a single
crystal consists of a set of diffraction spots on the film and the positions of these spots
depend on the orientation of the crystal. This is true of Laue method, transmission or back-
reflection, so either can be used to determine crystal orientation. However, the
backreflection method is the more widely used of the two because it requires nospecial

preparation of the specimen, which may be of any thickness, whereas the transmission
method requires relatively thin specimens of lowabsorption.
In either case, since the orientation of the specimen is to be determined from the location of
the Laue spots on the film, it is necessary to orient the specimen relative to the film in some
known manner. The single crystal specimens encountered in metallurgical work are usually
in the form of wire, rod, sheet, or plate, but crystals of irregular shape must occasionally be
dealt with. Wire or rod specimens are best mounted with their axis parallel to one edge of
the square or rectangular film; a fiducial mark on the specimen surface, for example on the
side nearest the film, then fixes the orientation of the specimen completely. It is convenient
tomount sheet or plate specimens with their plane parallel to the plane of the film and one
edge of the sheet or plate parallel to an edge of the film. Irregularly shaped crystals must
have fiducial marks on their surface whichwill definitely fix their orientation relative to
that of the film.
Single Crystal X-ray Diffraction:

•Accurate and rapid measurement of the position and intensity of the hkl reflections is
possible using single crystal X-ray diffraction.
•The methods available to detect X-ray do not record all the information about the
diffracted X-ray, only the intensity. The detectors are not sensitive to the phase of the X -
rays.
•Intensity is proportional to the square of the amplitude of the wave, thus the phase
information is lost. The phase information is related to the atomic positions in a crystal
structure, but...
•If the Bragg angles of the reflections are measured and indexed, the size of the unit cell,
information on translation symmetry elements, and symmetry information is obtained.
•The intensities (and position) of the reflections are different and these can be quantified
using a detector, CCD plate or scintillation counter, and recorded electronically.

X-rays interact with the electrons in the crystal, therefore a crystal with more electrons with
more strongly scatter X-rays.
•The effectiveness of scattering X-rays is called the scattering factor (or form factor) with
the symbol f .
•The scattering factor depends on the number o f electrons around the atom, the Bragg angle
θ, and the wavelength (λ) of the X-rays.
•The scattering factor depends on the number of electrons around the atom, the Bragg angle
θ, and the wavelength (λ) of the X-rays.
Powder Diffraction:
A powder may be composed of many small and finely ground crystals, known as
crystallites.
•These crystallites are (assumed to be) randomly oriented to one another.
•If the powder is placed in the path of a monochromatic X -ray beam, diffraction will occur
from the planes in those crystallites that are oriented at the correct angle to fulfill the Bragg
condition.
•The diffracted beams make an angle of 2q with the incident beam.

SOLVED PROBLEMS 01
146) The utilized reflecting plane of a sodium fluoride (NaF) analyzing crystal has a inter planner
distance of 1.5 A calculate the wavelength of the 2 nd order diffracted line which has a
glancing angle of 45
a.1.02
b.3.21
c.2.16
d.1.2
147) X-RAY wave length
a. 100-2-10nm
b. 1-2-10nm
c. 10-2-10nm
d. 10 2 -10nm

148) What are the advantages of synchrotron radiation over a lab x -ray source?
Ans- Synchrotron radiation is collimated, coherent, usually monochromatic and of
much higher brilliance compared to a lab source. The synchrotron beam can
deliver extremely high fluxes in a small area (typically a 20 micron beam for
instance).
149) What are the 3 reference frames (coordinate systems) of importance to the study of
orientation of crystals in an x-ray diffraction measurement?
a) Crystallographic Frame. b) Sample Fra me Machine direction/Transverse
Direction/Normal direction. c) Laboratory Frame of Reverence, NS EW.
03-01-02: APPLICATION
Applications:

Metals have found applications in thin-film technology due to their luster and high
electrical conductivity. Both properties are caused by the high mobility of electronic charge
carriers in the crystal lattice. Decorative and anticorrosion coatings of chromium, zinc and
derivative alloys for armatures, metal work, kitchen fittings, automotive parts, etc., are
mostly deposited by electroplating. The technique of gilding of jewelry, porcelain, relics,
etc., by gold leaf of only micrometers in thickness has been continuously developed for
more than 4000 years. Typical modern applications of thin metal films are Al layers of le ss
than 100 nm thickness used as barrier coatings on food packaging and as ref lective
coatings in light housings for automobile headlights to mention only a few examples.
Laterally structured thin metal films also play an enormous role in the semiconducto r
industry as electrical contacts between micrometer- and even submicrometer-sized devices.
For this purpose, metals are deposited by electroplating, chemical or physical vapor
deposition and subsequently structured by lithographic procedures to yield cond ucting plain
contacts and metal level connecting vias. Al plays a vital role in these applications, but a
severe problem that has to be addressed for metallic interconnects is electro migration
limiting the mean time to failure of integrated circuits. Due to its higher electrical
conductivity, Cu has recently partly replaced Al, as depicted in Fig. 1.18 where the highly
complex three-dimensional stacking of Cu layers is shown. Cu films deposited by
electroplating were found to exhibit a remarkable microstru ctural evolution after plating [.
Among the microstructural properties of interest in Cu interconnects are the texture and
grain size that can both affect the electromigration resistance. It should be mentioned,
however, that the introduction of Cu in the Si industry has been avoided for a long time,
because Cu is an extremely fast diffuser in Si and may severely degrade integrated circuit
performance by acting as a deep-level recombination center. The diffusion of Cu into the
semiconductor has to be safely prohibited by introducing anti-diffusion barriers, the
functionality of which has been effectively investigated using x -ray diffraction procedures
enabling their optimization Thin metal films are also of interest because of their mechanical
properties and various basic investigations have been performed with x -ray diffraction
techniques due to their model character for thin -film systems in general. Refractory Nb
films, for instance, are qualified by the high yield strength of Nb for engineering
applications and were found to exhibit pronounced depth dependencies during growth [6].
The same phenomenon was identified for titanium films that are applied as adhesion layers
for hard coating applications. Increasing attention has been paid in recent years to the
interesting plastic properties of nanocrystalline metals. For instance, plastic deformations in
electroplated nanocrystalline Ni films could be revealed by in situ investigations to be
reversible upon unloading instead of producing a residual dislocation n etwork [8]. X-ray
scattering investigations of thin metal films are used extensively to investigate grain sizes,

crystalline lattice faults, texture and residual stress. The various x -ray scattering techniques
to elucidate these microstructural features ar e outlined in the following chapters.
SOLVED PROBLEMS 02
150) sin45=
a.1/√2
b.1/2
c.0
d.1
151) How to produced x-ray ?
a. By heating electron by uv radiation.
b. Knocking only e-
c. Loss of inner shell e – one of the outer e– will fall into the vacant orbital with the
simultaneous emission of X-ray photon
d. None of the above.
152) ) a) Explain the difference between bremstralung radiation, white radiation and the
continuous spectrum. b) Are these radiations made in an X -ray tube? c) How or Why?
Ans- a) Bremstralung, white and continuous radiation are the s ame thing. b) c)
This refers to the spectrum produced by electrons as they impact the target
(anode) atoms and convert their momentum to X -rays in the process. Yes they are
made in the X-ray tube.
153) For the brass key run in the lab this week we use Vergard's law to determine the
zinc/copper content. Would you expect orientation of the crystals in this processed
sample to effect the results? What if the key contained a coating of chrome and we
wanted to determine the amount of chrome in the key?

Ans- Orientation will effect the relative intensity of diffraction lines, but since
Vergrad's Law does not use the relative intensity but the d -spacing, it is not
sensitive to orientation as long as the diffraction peak can be observed.
Determination of the amount of chrome will involve comparison of peak intensity
similar to the Moly/Copper measurement and will certainly depend on orientation
of the crystals in the processed key.
03-01-03: NEUTRON DIFFRACTION

SOLVED PROBLEMS 03
154) Bragg equation is
a. nλ=2
b. n=2d
c. nλ=2d
d. nλ=2f
155) What is the advantage of the neutron diffraction method compared to the X -ray
diffraction one?
Neutron diffraction can reveal the position of light element's atoms,
particularly when in the presence of heavier ones.
X-ray diffraction can reveal the position of light element's atoms,
particularly when in the presence of heavier ones.
There is no particular advantage
156) Give 3 differences between an electron beam and an x -ray beam that effect diffraction
Ans- Electrons have much lower wavelength, electrons are absorbed at a much
higher rate and they can generate secondary electrons and can charge a sample so
as to build up repulsion between the incident radiation and the sample. The
electron beam is focused and much smaller than the x -ray beam so that it can be
aimed at a single small grain. There are other differences.
157) What two kinds of spectroscopy (inelastic scattering) were di scussed that use x-rays as
the incident radiation. Give the difference between these two techniques.
Ans- XAS orXAFS and ESCA or XPS. X-ray absorption spectroscopy involves a
plot of absorption versus wavelength or frequency showing various absorption

edges and the lambda cubed decay in absorption with wavelength. XAFS can be
used to determine ionization states of metals. X -ray photoelectron spectroscopy
involves measurement of the number of photoelectrons ejected from the surface
by incident x-rays at various energies. This is used to characterize the chemical
composition of the surface.
03-01-04: ELECTRON DIFFRACTION

Electron Diffraction:
Do moving electrons display wave nature?
To answer this question you will direct a beam of electrons through a thin la yer of carbon
and analyze the resulting pattern.
Theory:
Louis de Broglie originated the idea that moving electrons may exhibit both particle and
wave nature. He proposed that, analogous to photons, the wavelength of the electron is
given by:
where h is Planck's constant and p = mv is the nonrelativistic electron momentum.

This experiment is an attempt to see whether electrons really do act like waves or whether
they always act like particles.
If electrons behave as particles (rigid spheres), the distribu tion of electrons will vary
continuously as a function of angle as in Figure 1. This distribution will vary only slightly
with changes in electron energy.
If electrons behave as a wave, however, a diffraction pattern will emerge. We can make an
analogy with the diffraction of x-rays by a crystal.
Review of x-ray diffraction:

Crystals act as three-dimensional gratings; they scatter the wave and produce observable
interference effects. In fact, x-rays scatter from the lattice planes (or Bragg planes) of the
crystal as shown in Figure 2.
There are two conditions for constructive interference of waves: 1. The angle of incidence
must equal the angle of reflection 2. The difference in path length must be an integral
number of wavelengths.
where n is an integer and is the order of diffraction.

By looking at the diffraction pattern and calculating the angle of diffraction, Bragg’s Law
allows us to determine either:
• the wavelength of the x-rays if the crystal structure is known, or
• the interatomic spacing of the crystal if the x-ray wavelength is known.
The second method is often used to determine the structure of an unknown crystal by
performing an x-ray diffraction experiment.
If electrons act like waves, we should be able to apply Bragg’s Law to the diffra ction of
electrons. In that case the beam would appear as concentric rings around a bright center.
This pattern can be thought of as a one -dimensional diffraction pattern of bright spots
rotated about its center.

The Experiment:
This experiment involves directing a beam of electrons through a carbon target, scattering
the electrons, and analyzing the pattern produced on a luminescent screen.
APPARATUS
THE ELECTRON GUN: The heater, cathode, and anode make up the electron gun.
Electrons are produced by heating a filament that is located inside an oxide-coated metal
“can” called the cathode. Electrons are ejected by thermionic emission from this heated
piece of metal (see Figure 4).
Once emitted, the electrons are accelerated by two pairs of anode rings. You apply an
adjustable acceleration potential Va (2000-4000 V dc) with the kilovolt power supply
between the cathode (-) and anode (+). This accelerates electrons to form an electron beam.
The beam will have kinetic energy equal to the change in electric pote ntial energy (eVa ). If
the beam velocity is non–relativistic (eVa<<mc2) we have at the anode:
CARBON TARGET As the electron beam passes into the anode, it strikes a very fine nickel
screen which holds vaporized graphite (carbon). The carbon suspension a cts as a
polycrystal, which means that the carbon consists of a large number of microcrystals that
are randomly oriented. This allows us to sample all possible angles of incidence without
changing the direction of the electron beam. If electrons act like a wave, different atomic
planes will produce constructive interference and the resulting electron diffraction pattern
will consist of concentric rings – one for each plane that satisfies the Bragg’s Law for
constructive interference, as in Figure 3. If elec trons act like particles the pattern will be as
shown in Figure 1. Diffraction caused by the nickel mesh may be neglected.
LUMINESCENT SCREEN: After leaving the target, diffracted electrons travel a certain
distance (L) and strike a phosphor screen. The screen is excited by the electrons, allowing
you to see the pattern made by the scattered electrons. Since the screen is inside a sphere,
you should use a flexible ruler to take measurements off the screen.
Procedure: Use the following diagram to connect the electron diffraction tube to its power
supplies.

CONNECTIONS:
Make sure all power is off (all equipment) before making any connections. Connect the
electron diffraction tube to the power supply as shown.
Connect the multimeter (ammeter) between the ano de and the positive side of the high
voltage power supply.
Set the multimeter to its current scale (mA) and turn it on. Make sure the high voltage
supply is set to its minimum. Turn on the power and wait for one minute for the cathode to
reach a stable temperature.
CONTROLLING THE CURRENT Normal operating current should be kept between 0.05 to
0.10 mA during measurements, and the voltage should be kept below 4.0 kV. Higher
currents can damage the carbon target. If it becomes necessary to exceed these levels , make
your measurements quickly and decrease the voltage as soon as you obtain your results.
DO NOT EXCEED 0.20 mA current. Slowly increase the high voltage until you observe a
pattern (around 2000 volts). Monitor the current closely.
SOLVED PROBLEMS 04
158) According to the Beer-Lamber's law, the absorbance of a sample is ____________ to
its molar concentration .
Inversely proportional
directly proportional
not related
159) Both NMR-spectroscopy and X-ray diffraction have been used for structural
analysis. What is the main difference between the information that the two techniques can
yield?
Simple one-dimensional NMR analysis of molecules in solutions does not yield details
on bond angles and lengths.
X-ray diffraction does not yield details on bond angles and lengths.

Both techniques yield the same results; choosing one or the other is a matter of
preference
160) Give the two examples of static and dynamic elastic scattering discussed in class
and describe the correlation function associated with each.
Ans- The examples given in class were x-ray diffraction and dynamic light scattering. The
correlation function for x-ray diffraction is the pairwise correlation function of electron
density in space and for dynamic light scattering it is the time correlation function for
fluctuations in intensity.
161) The diffusion of atoms is extremely rapid with the mean free path (average
translation) of about 0.1 mm or one million times their size, while colloids move slowly
with mean free paths on the order of their size at best. Explain how this effects the
difference between XRD and small-angle scattering
Ans- Colloids can't really form crystals from a kinetic perspective even if they had perfect
structure. They can't probe enough arrangements due to slow motion to find an energy
minimum on any reasonable time scale. This means that the structure factor will be
dominated by defects and disorder despite some tendency to form crystals.
162) Express the wavelength λ of the electron as a function of the accelerating potential
Va -- using the de Broglie relation (1) and relation (3).
163) Equate the wavelength λ in questions 2 and 3 and solve for D. Show that D is
proportional to
CHECK POINT 03-01
1) Which of the listed compounds would be best suited for the EPR analysis?
35 37 79
2) Chlorine and bromine have two isotopes each: Cl (76), Cl (24), Br (51),
81
and Br (49). What peak (mass-to-charge ratio, m/z) in the MS spectrum of
ClBr 3 would correspond to the heaviest molecule?
3) What is mass spectrometry used for?
4) You are given a sample of naphthalene crystals and asked to select an analytical
method to determine its mass percent composition . Choose the appropriate method:
SUMMARY
X-ray diffraction has contributed more to mineralogical characterization of clay fractions of
soils than has any other single method of analysis. X -ray photons may be considered as
"packets" of monochromatic electromagnetic waves, generated as random events, emanating
outward in a spherical array from their point source. Commercial x -ray diffraction
equipment includes a high-voltage generator, an x-ray source, an x-ray beam collimating
system, and a detecting and recording system. Crystal monochrometers for selective
discrimination of diffracted x-rays from nondirectional x-ray scatter are available for use
with recent x-ray spectrometers. Qualitative interpretation of diffraction patterns involves
identification of crystalline species from the array of diffraction maxima obtained from a
sample. For the most reliable and accurate estimation, the use of x -ray diffraction analysis

in conjunction with other methods such as differential -thermal, integral-thermal, infrared,
surface-area, elemental analysis, and other species -specific chemical methods is advisable.
KEY WORDS
Chemical biology, Structural biology, Techniques & methods ,MAD phasing
Crystallography ,SADMultiple wavelength anomalous diffraction,
REFERENCES
Alexander, L. E. & Klug, H. P. (1948). Anal. Chem. 30, 196.Google Scholar
Chung, F. H. (1975). J. Appl. Crystallogr. 8, 17.CrossRefGoogle Scholar
Copeland, L. E. & Bragg, R. H. (1958). Anal. Chem. 30, 196.CrossRefGoogle Scholar
Davis, B. L. (1986). Reference Intensity Method of Quantitative X-ray Diffraction
Analysis, South Dakota School of Mines and Technology.Google Scholar
Garbauskas, M. F., & Goehner, R. P. (1982). Adv. X-Ray Anal. 25, 283.Google Scholar
1) a metalloenzyme containing Cu
2) 280
3) to detect the masses of molecules and their fragments
4) CHN analysis
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=z_8aJPLr21E
https://www.youtube.com/watch?v=AqCz_b7VJK8
WIKIPEDIA
https://www.sciencedirect.com/topics/chemistry/diffraction -method
https://en.wikipedia.org/wiki/Neutron_diffraction
https://en.wikipedia.org/wiki/Electron_diffraction
OER
____
REFERENCE BOOKS
1. X-RAY DIFFRACTION: ITS THEORY AND APPLICATIONS - By S. K.
CHATTERJEE
2. Diffraction Analysis of the Microstructure of Ma terials - edited by Eric J.

Mittemeijer, Paolo Scardi

03-UNIT 02: RAMAN SPECTROSCOPY
LEARNING OBJECTIVES
 Describe classical and quantum mechanical theories of Raman effect.
 State selection rules in Raman spectroscopy.
 Discuss Mutual exclusion Principle with suitable examples.
 Explain complementary nature of Raman and Infrared spectra.
 Apply Raman and Infrared spectra in structure determination.
 Define the Instrumentation and sample handling in Raman spectra.
1) INTRODUCTION:
When a beam of light falls on a substance, it may be transmitted, absorbed on scattered. If

the substance is transparent and does not absorb in the visible region of the electromagn etic
spectrum, nearly all of this light is transmitted. A small fraction of the incident light,
however emerges in all directions as a result of scattering. If the light is monochromatic,
nearly all of the scattered light is observed to be of the frequency as the incident light. This
is called Rayleigh scattering. But on longer exposures, we find that light of discrete
frequencies above and below the incident frequency is also scattered. This phenomenon is
referred to as Raman scattering, after its discover er C. V. Raman. A. Schematic
representation dissociation of a Raman spectrum is shown in the figure given below:

where the subscripts I,R and mol refer to the incident light, the Raman line and the
molecule respectively. The vertical lines indicate t he absolute value of the corresponding
difference.
03-02-01: CLASSICAL THEORY OF RAMAN EFFECT & QUANTUM THEORY OF

RAMAN EFFECT
1) CLASSICAL THEORY OF RAMAN EFFECT:
Some understanding of Raman scattering may be obtained from classical theory. They
basic to Raman Effect is the concept of polarizability of a molecule. When a molecule
is placed in a static electric field it undergoes some deformation, the electronic cloud
being attracted to the positive pole of the field and positively charged nuclei to the
negative pole.This separation of charge gives rise to an induced dipole moment, and
the molecule is said to be polarized.The magnitude of depends on the intensity of
the electric field E and on the ease of deformibility or polarizability, of the molecule.
When a sample of molecules is subjected to a beam of radiation of frequency ,

each molecule in it experiences an electric field which varies according to the
equation.
According to electromagnetic theory an oscillating dipole emits radiation whose

frequency is the same as its oscillation frequency. Equation (3.3) thus gives the
classical explanation of Rayleigh scattering. Moreover, if the molecule itself
undergoes some motion like vibration or rotation, which changes the polarizability

periodically, then the dipole (oscillating with the frequency of the applied field) will
have superimposed on it vibrational or rotational oscillation.
For example let us consider a vibration of frequency polarizability. For small

displacement from the equilibrium distance, the polarizability can be expressed as
, From equation (3.5) it is clear that the existence of Raman lines depends on  change
in polarizability with the vibration. The corresponding spectrum is called vibrational
Raman spectrum. Similarly, the change in polarizability during the molecular rotation
also leads to a rotational Raman spectrum, in which the shifts from the Rayleigh line
are related to rotational frequencies. Thus, we see that in order to be Raman active a
molecular vibration or rotation must cause a change in the polarizability of the
molecule. In contrast to this the condition for infrared and microwave activity, is that
the molecular motion must produce a change in the electric dipole moment of the
molecule.
Although, the conclusions drawn from Eq. (3.5) are to a considerable extent in good
agreement with experimental observations of Raman spectra. However, there is a
marked disagreement as well. Eq. (3.5) predicts that the pair of Raman lines with the
same absolute value of the frequency shift would appear in the spectrum with equal

intensity while, it is found that the lines an high frequency side of the Rayleigh line
are very weak compared to those on the low frequency side. This is well explained
when we consider quantum theory of Raman effect.
2) QUANTUM THEORY OF RAMAN EFFECT:
as a streamFrom quantum theory, we can consider the incident light of frequency of
particles (called photons) each having energy , where h is Planck constant. These
photons are imagined to undergo collisions with molecules. If the collisions are
perfectly elastic, there will be no exchange of energy between the molecule and the
striking photons and the latter will be simply detected unchanged. A detector placed at
right angles to the incident beam will thus record photons of energy . However,
some collisions may also result in exchange of energy between molecule and photon,
and then they are called inelastic.
Schematically, these processes can be shown in the figure given below :
We may imagine that for the extremely short period that a photon is near a molecule
during the collision the two form a sort of complex having an energy different from
that of any molecular energy level. After the photon has moved away, it is most likely
that the molecule will return to the level where it was before colliding with the photon
[Fig. (a)]. In such a case the photon energy is not changed by collision, and Rayleight
scattering occurs. There is also a small probability that, if the molecule was initially
on the lowest vibrational level (v = 0) after interaction with a photon it will in the next
higher vibrational level (v = 1), as shown in figure (b). The scattered photon in this
case will have lost some energy equal to the energy gained by the molecule and will
consequently be if lower frequency. There is again a very small probability that a
molecule, which is initially in the v=1 level will after interaction with a photon move
to the v=0 level (fig. (c)). The energy lost by the molecule is gained by the scattered
photon, which therefore has a higher frequency. The last two situation pertain to
Raman scattering. At ordinary temperatures, only a small number of molecules can be

in the v=1 level, while majority of them exist in the v=0 level. It is therefore easy to
predict that for a pair of Raman lines having the same value of the frequency shift , the
line with frequency higher than the incident frequency will be weaker than the one
with the reduced frequency
SOLVED PROBLEMS 01
Author should provide here about 2-3 solved problems, on this Unit topics.
164) For acetone a normal mode of vibration that involves the stretching of the carbonyl
band is active in both Raman infrared spectra. The Raman line associated with this
normal mode is found at 547 nm when excited by incident light show wavelength is
500 nm. Calculate the wavelength of the centre of corresponding infrared absorption
band.
a. Solution:
165) For CO2 the following spectroscopic data are available. Predict the geometry of CO2
molecule
a. Solution: Analysis of the given data is as follows
a. Since transition at 2349 cm–1 includes PR contour,
we may conclude that the molecule CO2 is linear
b. The infrared and Raman spectra do not include any
common line and hence the molecule of CO2 contains

the cenre of symmetry. Hence structure of CO2 is : O
=C=O
166) WHAT IS RAMAN SPECTROMETER ?
Raman spectrometer is an instrument that consists of one or more single -
coloured light sources and lenses and filters to focus the light and to
differentiate the reflected and scattered light, respectively. A prism is used
for splitting the light into its components which has a detector to detect the
weak light. Later the spectrum is obtained on the monitor to analyze the
information.
167) WHAT IS RAMAN SPECTRA?
To analyse the Raman effect, the wavelength of the scattered photon is
converted to wavenumber. These wavenumbers are plotted on the x -y
plane. The wavenumbers are taken along the x -axis and the Raman
intensity is taken on the y-axis. The difference between the wavenumbers
and the intensity is known as the Raman spectrum.
168) What is the essential condition for Raman shift in scattering ?
169) In CO2 no vibration is simultaneously active in both Raman and IR, while in H2O
molecule the vibrations are active both in Raman and IR spectra. Exp lain it.
03-02-02: PURE ROTATIONAL AND VIBRATION RAMAN SPECTRA

1) PURE ROTATIONAL RAMAN SPECTRA:
For a complete treatment of the Raman scattering, quantum mechanical perturbation
theory must be applied. The rotational selection rule which is derived from thi s
theory is in contrast to the corresponding selection rule for microwave
spectroscopy
In Raman work the rotational quantum number changes by 2 units rather than one is
related to the fact that the molecular polarizability, in contrast to the permanen t
dipole moment; is not a vector quantity, and so in every complete rotation, it returns
twice to its original value. Thus the polarizability changes with a frequency which is
twice the rotational frequency of the molecule.
The expression for rotational energy levels of linear molecules has already been
stated.
where J is the rotational quantum number in the lower state. Since

we may refer to the lines arising from these energy changes as S branch lines this is
indicated by putting subscript S.
If the molecule gains an amount of rotational energy as given by Eq (3.7), from a
photon during collision, we get an S-branch line on the low wave number side of the
exciting line. This is therefore a stokes line. The wave number (in cm –1) of Stokes
lines are consequently given by :
is wave number (in cm–1) of exciting radiation. The corresponding equation for anti
Stokes lines of the S- branch is, evidently
where, as before, J is the rotational quantum number in the lower state.

The allowed transitions and the Raman spectrum arising are shown in the figure
given below.
The relative intensities depend on the relative population of the rotational levels as
given below

Since many rotational levels are populated, downward transition are quite as likely as
upward ones, and consequently Stokes and anti - Stokes lines are comparable in intensity.
From equation (3.8) & (3.9) it is seen that the frequency separation of the first Stokes or
anti - Stokes line (which corresponds to J = o) from the exciting line is 6 B cm–1, while
the separation between successive lines on either side of the exciting line is 4 B cm –1.
From spectrum we can thus immediately obtain a value of B (i.e. B/c) and from it the
moment of inertia (I) and bond length.
Homonucelar diatomic molecules (e.g. O2, H2) give neither infrared nor microwave
spectra since they possess no dipole moment. But such molecules do give a rotational
Raman spectra. So, now for the first time we have seen a method for obtaining molecular
parameters of homonuclear diatomic molecules. It is thus complementary microwave to
mirror wave and infrared studies, not merely confirmatory.
The alternate rotational levels of linear molecules like O2, CO2, which are composed of
nuclei with zero spin and have a centre of symmetry are co mpletely unoccupied. This is
revealed in the Raman spectrum by the absence of alternate spectral lines. For example in
the case of O2, every level with an even value of J is empty and so the transition which are
labelled J = 0, 2, 4 ... in the figure will be missing from the spectrum of O2. This leads to
aline spacing of 8B in stead of the usual 4B discussed above. On the other hand, in the
case of molecules containing nuclei with non zero spin and having a cenre of symmetry
(e.g. H2,.H—C C—H) the spectral lines show a strong weak, strong weak ..alternation in
intensity.
In the case of symmetric top molecules (e.g. CHCl3) rotation about the top axis produces
no change in polarisability but end -over-end rotations do produce such a change. For such
molecules we have the energy levels

Thus in the Raman spectrum of a symmetric top molecule, we shall have two series
of lines of frequencies.
It follows then that the lines in the R Branch will be 4B , 6B , 8B , 10B ... cm –1
from the exciting line, while the S branch lines will occur at 6B , 10B , 14B ... cm–
1. Clearly every alternate R-line will be overlapped by an S-line and complete
spectrum will thus be expected to show a marked alteration in intensity.
In the case of spherical top molecules (e.g. CH4, SiH4) the polarizability does not
alter with rotation. So pure rotation of spherical top molecule are Raman inactive.
Bond lengths in such molecules must therefore be obtained from the line structure of
vibration rotations spectra.

All rotations of asymmetric top molecules, on the other hand are normally Raman
active and in consequences of this their Raman spectra are quite complicated.
2) VIBRATIONAL RAMAN SPECTRA:
The structure of vibrational Raman spectra can be discussed easily. For every
vibrational mode we can write an expression for energy (in cm–1) as
Quite general, too, is the selection rule:
Which is the same for Raman as for infrared spectroscopy the probability of
Since as we saw earlier, vary few of the molecules exists in the v=1 state at ordin ary
temperatures, the anti Stokes lines will be normally expected to be much weaker
than Stokes lines.
The vibrational Raman spectrum of a molecule is then basically simple. It will show a
series of reasonably intense lines of the low frequency side of the exciting line with a much
weaker mirror image series on the high frequency side. The separation of each line from the
centre of the exciting line gives immediately the Raman active fundamental vibration
frequencies of the molecule.
When the chemical formula of a given molecule is known, we can predict for each
symmetry group, to which the molecule might belong, the number of normal vibrational
modes that will be Raman active and infrared active. A comparison of the Raman spectra

and infrared spectra with the predicted pattern then reveals whether the assumed symmetry
group is the correct one.
For example, let us consider the AB3 type molecules. In general, we would expect for them
( 3 × 4 –6 )= 6 normal modes of vibration. The two simplest possible shapes f or this type of
molecules are symmetric plane (symmetry group D3h) or regular pyramidal (symmetry
group C3v). For both planar and pyramidal shapes, one stretching mode and one bending
mode are each double degenerate and so only four different fundamental f requencies should
be observed. Now, if the AB3 molecule is planar, it can be predicted that of the four
observable frequencies one should appear only in the Raman spectrum, one only in the
infrared spectrum and two in both Raman and infrared spectra. For a pyramidal AB3
molecule, however, it can be predicted. That all normal modes are both Raman and infrared
active, and so all four different fundamental frequencies should appear in both Raman &
infrared spectra. Let us take the nitrate ion (NO3 –) and the chlorate ion (ClO3 –) as
examples. That the observed spectra are consistent with a planar structure for NO3 – and a
pyramidal one for ClO3 – is shown by the data given in table below :
3) VIBRATIONAL-ROTATIONAL RAMAN SPECTRA:

We need not consider in detail the vibrational rotational structure of Raman spectra
in general because such rotational fine structure is rarely resolved, except in the
case of diatomic molecules. So, a study of only diatomic molecules will be
undertaken here. The vibration rotation energy states for diatomic molecules are
given by:

Stokes lines (i.e. lines to low frequency of the exciting radiation) will occur at wave
numbers given by
The spectrum arising is sketched in figure given below where for completeness, the
pure rotation lines in the immediate vicinity of the exciting line are also shown :
The presence of the strong Q branch in the Raman spectrum is to be noted and compared
with the P and R branches only which occur for a diatomic molecule only in the infrared.
The analysis of O and S branches in the Raman spectrum to give a value for B and hence
for the moment of inertia (I) and bond length is straight forward
Much weaker anti-Stokes lines will occur at the same distance from, but to high frequency
of, the exciting line.
For larger molecules, we ignore the rotational line structure since it is not resolved. Even
the O and S (or O, P, R, & S) band contours are seldom observed since they are very weak
compared with Q branch. Thus while the infrared spectrum of chloroform (CHCl 3) shows
distinct PR or PQR structure on some bands, the Ramssan spectrum, with the possible
exception of the band at 760 cm–1, shows only the strong Q branches. While some
information is denied us in Raman spectra because of this, it does represent a cons iderable
simplification of the overall appearance of such spectra.

The above information on bond lengths and vibration frequencies have been obtained from
vibrational rotational Raman spectra. In the case of CS2 and CH4 the symmetrical
stretching modes only are given since the wavenumber of the other modes are determined
from infrared techniques.
4) SELECTION RULES IN RAMAN SPECTROSCOPY:

The reason for the difference in the two phenomenons is due to different conditions that are
required in the two cases. In the direct absorption effect, the presence of a dipole moment
or change in the dipole moment is necessary, while in Raman effect other factors such as
optical anisotropy, change of the polarizability or refractivity of the molecule prevail.
Thus a rotational Raman line occurs only when the molecule involved is optically
anisotropic. The greater the anisotropy, greater is the intensity of rotational Raman line.
Thus, electrically non polar, but optically anisotropic molecules such as H2, N2, O2 etc.
give rise to pure rotational Raman lines, but they to not have corresponding far infrared
absorption lines. A vibrational Raman line occurs when the mode of oscillation involved
causes a change in the polarisability of the molecule. Greater the polarizability of molecule,
greater is the intensity of the vibrational Raman lines. Thus the molecules such as NO2,
CS2 and CO2 in which symmetric oscillations occurs, cause no change in dipole moment
but gives rise to intense vibrational Raman lines due to large variat ion in then polarisability
involved,. Such lines do not correspond to any infrared a absorption lines.
The study of Raman effect in N2 and O2 has confirmed the verification of the selection
. Similarly, the analysis of the Raman spectra of HCl gas led t o the same
conclusion as far as selection rules are involved in the origin of Raman lines.
5) MUTUAL EXCLUSION PRINCIPLE:
In a molecule with a centre of symmetry, it has been observed that those vibrational modes
which are Raman active are infrared-inactive and infrared active modes are Raman inactive.
This is called the mutual exclusion Principle. All homonuclear diatomic molecular (e.g. H2,
O2, N2 etc.) have a centre of symmetry and consequently are Raman active only.

Similarly in benzene C6H6 (D6h) out if 30 normal modes of vibration, eight vibrations are
silent fundamental vibrations. It must not be concluded from these examples that any
molecule with a centre of symmetry will possess one or more totally inactive modes. For
example, in the complex [Pt Cl 2 Br2]2– has a centre of symmetry and belongs to D2h point
group but has no silent vibration. Out of its nine modes of vibration six are infrared active
and rest three are Raman active. So more precise and clear rule of mutual exclusion can be
stated as for a molecule with a centre of symmetry, any given normal vibration may be
active in infrared or in Raman (or in neither) but not in both. This is very important
generalization, making an explicit possibility of spectroscopically silent vibrations a nd is of
immense help in structure determination of molecules.
SOLVED PROBLEMS 02
170) Raman effect is a scattering of ---------
1. Atoms
2. Molecules
3. protons
4. photons
171) To what type of electromagnetic radiation is a sample exposed in Raman

spectroscopy?
Ultra-violet
Visible
Infrared

172) Why do the anti-Stokes lines of carbon tetrachloride have the following order of
intensity: 218 > 314 > 459 cm -1 ?
I suggest that they consider the energy level diagram and think about the
transitions that correspond to each of these. They can rationalize that the

line for the 218 cm -1 band originates by forming a virtual state from the
most populated vibrational level and the band for 4 59 cm -1 from the least
populated vibrational level, which explains the relative intensities.
173) What would be the ideal source to use for measuring Raman spectra?
They can usually come up with resolution and sensitivity. I remind
them that Raman scatter is a weak process. They realize that a high powered laser will
provide better sensitivity than a continuum source They already know that lasers are highly
monochromatic and realize that this is another reason to use a l aser .
174) Compare Raman and Infrared spectra.
175) Explain mutual exclusion principle with suitable example.
03-02-03: COMPLEMENTARY NATURE OF RAMAN AND IR

SPECTRA
If the molecule has a centre of symmetry the modes active in Raman spectra are inactive in
infrared spectra and vice versa, so that Raman and infrared spectra are completely
complementary. Raman spectroscopy and infrared spectroscopy are methods for
determining the internal vibration of molecules, and their use in analysis is based on the
specificity of these vibrations.
In general, the strong bands in the infrared correspond to weak bands in the Raman and vice
versa. This complementary nature of infrared and Raman spectra is due to the electrical
characteristics of the vibration. The factor that determine s whether or not a bond is
absorbed in the infrared or Raman spectrum is the electrical nature of the normal vibration.
For a band to be allowed in the infrared, the normal mode must produce a change in dipole
moment during vibration, while for a band to be allowed in the Raman spectrum there must
be a change in the polarizability of the molecule during the vibration. For example, in the
symmetrical stretching mode of benzene at 991 cm–1, the molecule suffers no change in
dipole moment but there is a change in the polarizability. Hence this vibration is infrared
inactive but Raman active.
Thus infrared and Raman selection rules are mutually exclusive, that is a band allowed in
the infrared is forbidden in the Raman and vice versa. This condition is true for all
molecules which have a centre of symmetry.
In Molecules with different elements of symmetry, certain bands may be active in Raman,
infrared, both or neither. For a complex molecule that has no symmetry element except
identity all of the normal modes are allowed both in Raman and infrared spectra. But the
infrared & Raman spectra of a compound do not necessarily exhibit the same bands
differing only in intensity.
Vibrations involving polar bonds such as C—O, N —O, O—H etc. are comparatively weak
Raman scatters because if a bond is strongly polarised there is a small change in its length
during a vibration and it will have only a small additional effect on the polarisation. Such
polarized bonds, however, carry their charges with them during the vibrational motion, and

unless neutralised by symmetry factors, result in a large net change in dipole moment and
high infrared intensity.
C, C—H etc. suffer larger changes in relatively neural bonds such as C—C, C = C, C
polarizability during a vibration. The dipole moment is not affected and vibrations that
predominantly involve this type of bonds are strong Raman scatters but weak in infrared.
3) STRUCTURE DETERMINATION FROM RAMAN AND INFRARED
SPECTROSCOPY:
The combined use of Raman and infrared spectroscopy helps us to determine the shape
of some simple molecules. The molecules that have been chosen to illustrate the
principles are CO2, N2O, SO2, NO3 –, ClO3 – and ClF3.
Let us consider first the triatomic AB2 molecules, the questions to be decided are
whether each molecule is linear or not and if linear whether it is symmetrical (B -A-B)
or asymmetrical (B-B-A). In the case of carbon dioxide (CO2) and nitrous oxide
(N2O), both molecules give rise to some infrared bands with PR contours; they must,
therefore, be linear. The mutual exclusion principle shows that CO2 has a centre of
symmetry (O— C—O) while N2O has not (N-N-O) since only the later has bands
common to both its infrared and Raman spectra. Thus the structure of these molecular
are completely determined. The infrared and Raman absorption of SO2 are given in the
table below :
We see immediately that the molecule has no centre of symmetry, since all three
fundamentals are both Raman and infrared active. In the infrared all the three samples
show very complicated rotational fine structure and it is evident that the molecule is
non linear no band shows the simple PR structure of, say carbon dioxide. The
molecular has, then the bent shape:
The AB3 type molecules require rather more discussion. In general we would e xpect
3N- 6 = 6 fundamental vibrations for these four atomic molecules. However, if the
molecular shape has some symmetic this number will be reduced by degeneracy. In
particular, for the symmetric planar and symmetric pyramidal shapes, one stretching
mode and one angle deformation mode are each doubly degenerate and so only four

different fundamental frequencies should be observed. These are given in the table
below where their various activities and band contours or polarisaion are also
collected. Both molecular shapes are in fact symmetric tops with three fold axis (C3)
passing through atom A perpendicular to the B3 plane. It is with respect to this axis
that the vibrations can be described as II or

SOLVED PROBLEMS 03
176) Which of the following cannot be conserved during Raman scattering?
a)Total energy
b)Momentum
c)kinetic energy
d)electronic energy
177) The elastic scattering of a photon is called?

a)atmospheric scattering
b)Rayleigh scattering
c) Conserved scattering
d)Raman scattering
178) What is Principle of Raman Spectroscopy?
The principle behind Raman spectroscopy is that the monochromatic radiation
is passed through the sample such that the radiation may get reflected,
absorbed, or scattered. The scattered photons have a different frequency from
the incident photon as the vibration and rotational property vary. This results in
the change of wavelength,, which is studied in the IR spectra.
The difference between the incident photon and the scattered photon is known
as the Raman shift. When the energy associated with the scattered photons is
less than the energy of an incident photon, the scattering is known as Stokes
scattering. When the energy of the scattered photons is more than the incident
photon, the scattering is known as anti-Stokes scattering.
179) With which types of spectroscopy would one observe the pure rotation spectrum of H2.
If the bond length of H2 is 0.0741 nm, what would be the spacing of the lines in the
spectrum?
180) Write selection rules for vibrational rotational Raman spectra.
03-02-04: INSTRUMENTATION AND SAMPLE HANDLING

Raman spectroscopy is essentially emission spectroscopy and the bulk of the
instrumentation is simply a typical visible region spectrometer the distinguishing
characteristic of Raman work of course, is the exciting source.
Then invention of accessible and relatively inexpensive laser sources in last few years has
made a major revolution in Raman techniques, by largely replacing the traditional mercury
discharge lamp as an exciting source. Previously the process of obtaining a good Raman
spectrum of anything required 10-20 ml of sample and was often a very time consuming
operation. Now Raman spectra of virtually all samples can be run on a completely routine
basis using one milliliter or less of sample and taking a few minutes only.
In fact the laser is almost ideal as Raman source. It gives a very narrow, highly
monochromatic beam of radiation, which may be focused very finely into a small sample,
and which packs a relatively large power from several milliwatts to a few watts depending
on the type of laser into its small frequency spread.
We can compare the two excitation techniques the mercury discharge lamp in the form of
spiral round the sample. This forms of excitation pumps a good deal of energy into the
sample. But is spread over the many emission lines of the mercury vapor notably 435.8 and
253.6 nm. It suffers from three main disadvantages.

i. The extended source allows a good deal of the exciting radiation to be scattered
directly into the spectrometer where it masks all the Raman lines less than e ) same
100 cm–1 from the exciting frequency
ii. (ii) The sample tube needs to be about 20 -30 cm long and 1-2 cm in diametre, so
that a considerable quantity of sample is required
iii. The relatively high frequency of the mercury radiation often causes the sample to
fluoresce and the resulting florescence spectrum swamps the very weak Raman
spectrum.
Nonetheless the mercury lamp is often still preferred for gaseous samples, where a large
sample tube can have a very carefully mercury lamp built round it, and thus collect the
exciting radiation with maximum efficiency. The laser beam directed -through a sample and
caused to undergo multiple passes, by means of mirrors can be shown in the figure given
below
Only three such passes are shown in the figure but by careful alignment of the mirrors upto
10 passes may be achieved, thus enhancing the Raman signal. The standard sample
container is a box of quartz about 2 cm long and 0.5 cm2 in cross sec tion provided with
filling parts its capacity is thus 1 ml. The quantity of sample required can be reduced
considerably, however, by using a thin capillary tube, filled with sample and sealed at one
end, with laser beam directed along its length. Now a few microliters of liquid give a
spectrum of about 60 percent of the intensity of that from a 1 ml sample with multiple
traverse. Solids, in powder or transparent block form, are equally stable for laser excitation.
Further laser typically operate at frequencies lower than that of the mercury lamp (e.g. the
He-Ne laser, at 632.8 nm and the argon laser at 514.5 and 488.0 nm) and are thus very much
less likely to cause the sample to fluoresce. Also if one particular laser does produce

fluorescence, it is simple matter technically to switch to another lesser and run a successful
Raman spectrum.
Finally the Rayleigh scattering is much diminished with the very confined laser beam and it
is routine to defect Raman scattering to within some 20 cm–1 of the exciting line. Radiation
scattered from the sample is directed, via mirrors, into spectrometer operating in the visible
region. The monochromator is either a quartz prism or a grating and the radiation is
detected, in the case of laser instrument, by a photoelectric d etector with its output fed an
amplifier and pen recorder. Instruments using a mercury discharge lamp as exciting source
may also use a photomultiplier and pen recorder, but they gave, in addition, provision for
the insertion of photographic plate as detector, since the weakest of Raman lines may be
observed by allowing the exposure to continue for many hours or even several days.
SOLVED PROBLEMS 04
181) How many degrees of freedom does a chemical compound of N atoms have?
a)2N
b)2N+1
c)3N
d)3N+1
182) In Raman spectroscopy, the radiation lies in the-------
a) microwave region
b)visible region
c)UV region
d)x-ray region

183) What Is Applications Of Raman Effect?
a)Raman amplification: this is based on the Raman scattering where the
lower frequency photons are pumped to a high -frequency regime with a
surplus amount of energy. This method is applicable to
telecommunications.
b)Supercontinuum generation: In optics, supercontinuum is formed using
the Raman spectra, which results in smooth spectra as the initial spectra
are built spontaneously which is later amplified to higher energy.
c)Raman spectroscopy works on the basis of Raman effect and finds
applications in various fields like in nanotechnology to understand the
structure of nanowires, in biology and medicine where the low -frequency
DNAs and proteins are studied and chemistry to understand the structure
of molecules and their bonds.
d)Raman scattering is used in remote sensing and planetary exploration.
e)Raman scattering is used to sense the minerals in Mars.
184) Define Raman scattering? What are the types of Raman’s Spectroscopy?
Raman scattering is defined as the scattering of photons by the excited molecules that are at
higher energy levels. Resonance Raman Spectroscopy ( RRS), Surface-enhanced Raman
Spectroscopy (SERS), Micro-Raman Spectroscopy, Non-linear Raman Spectroscopic
Techniques
CHECK POINT 03-02

1) Raman effect is produced by which one of the following process of
spectroscopy?

2) Zeeman effect is the splitting of spectral line in the presence of _______
3) Which one of the following types of spectroscopy is a light -scattering technique ?
4) The source of radiation used in Raman spectroscopy is _______
SUMMARY
Light interacts with tissue in a number of ways including, elast ic and inelastic scattering,
reflection and absorption, leading to fluorescence and phosphorescence. These interactions
can be used to measure abnormal changes in tissue. Initial optical biopsy systems have
potential to be used as an adjunct to current investigative techniques to improve the
targeting of blind biopsy. Future prospects with molecular-specific techniques may enable
objective optical detection providing a real -time, highly sensitive and specific measurement
of the histological state of the tissue. Raman spectroscopy has the potential to identify
markers associated with malignant change and could be used as diagnostic tool for the early
detection of precancerous and cancerous lesions in vivo. The clinical requirements for an
objective, non-invasive, real-time probe for the accurate and repeatable measurement of
pathological state of the tissue are overwhelming. This paper discusses some of the recent
advances in the field.
KEY WORDS
Oils and fats; FT-Raman spectroscopy; chemometrics
REFERENCES
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ATR-FTIR spectroscopy. Vib. Spectros 2009, 49, 64–67. [Google Scholar]
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Allibone, R.; Dias-Gunasekara, S. Infrared microscopy of epithelial cancer cells in whole
tissues and in tissue culture, using synchrotron radiation. Faraday Discus 2004, 126, 27–39.
[Google Scholar]
3. De Gelder, J.; De Gussem, K.; Vandenabeele, P.; Moens, L. Reference database of Raman
spectra of biological molecules. J. Raman Spectrosc 2007, 38, 1133–1147. [Google Scholar]
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microfluorometry. Biophys. J 1996, 71, 2158–2167. [Google Scholar]

1) Molecular vibration
2) Magnetic field
3) Raman
4) Junable mercury–neon laser lamp
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=ncyvjov3H4g
https://www.youtube.com/watch?v=pXVS0Q0WuUY
WIKIPEDIA
https://en.wikipedia.org/wiki/Raman_spectroscopy
https://www.sciencedirect.com/topics/chemistry/polarized -raman-spectrum
OER
____

REFERENCE BOOKS
1. Fundamentals of molecular spectroscopy; C.N. Banwell, (Tata McGraw Hills)
2. Molecular Spectroscopy; P. S. Sindhu (Tata McGraw Hills)
3. Spectroscopy; B. K. Sharma Goel Publishing House Meerut, U.P.
4. Organic spectroscopy, William Kemp; ELBS/Macmillan.

CREDIT 03-UNIT 03: ESR SPECTROSCPOY THEORY
LEARNING OBJECTIVES
 To make the student acquainted with paramagnetic species such as free radicals.
 To their identification using the technique of electron spin resonance (e.s.r.)
spectroscopy.
INTRODUCTION
1 INTRODUCTION:
Electron spin resonance (ESR), also called electron paramagnetic resonance (EPR), is a
spectroscopic technique confined to the study of species having one or more unpaired
electrons.
Among the large number of systems having one or more unpaired electrons, i.e.
paramagnetic system, the most important ones are free radicals, transition metal ions, ions
and molecules having odd number of electrons.
03-03-01: PRINCIPLE BEHIND ESR SPECTROSCOPY
An electron spins on its own axis and its spin quantum number, . The spin motion of
an electron gives rise to spin angular momentum, S given by
This spin angular momentum vector can take only those orientations in the presence
of an external magnetic field, in which its components along the direction of the external
magnetic field (along z-axis) are half-integrals.

The frequency falls in the microwave region of electromagnetic spectrum. Hence,
microwave source and techniques have to be applied to record ESR spectra.
SOLVED PROBLEMS 01
185) Electron spin resonane is observed for hydrogen atom with an instrument operating at
9.5 GHz. If g value for electron in hydrogen atom is 2.0026, wha t is the magnetic field
applied? Bohr magneton,
186) Which of the following will NOT show electron spin resonance (ESR)?
(A) Free radicals
(B) Paramagnetic materials
(C) Transition metals
(D) Diamagnetic materials
187) What is application of esr?
a) Study of free radical including reaction velocity and mechanism.
b) Structure elucidation of organic and inorganic molecules.
c) Study of biological system using spin labelling technique.
d) Quantitative analysis:- It is done in instrument having dual sample
cavity.
188) Discuss the principle behind ESR spectroscopy. What type of specie s are studied by
this technique?
189) What is Principle of ESR?
The phenomenon of electron spin(ESR) is based on the fact that an electron is a charged
particle it spins around its axis and this causes it to act like a tiny bar magnet
1. When a molecule or compound with an unpaired electron is placed in a strong
magnetic field

•The spin of the unpaired electron can align in two different ways creating two spin
states ms = ± ½
2. The alignment can either be along the direction (parellel) to the magnetic filed
which corresponds to the lower energy state m s = - ½• Opposite (antiparallel) to the
direction of the applied magnetic field
mrs=+1/2
3. The two allignments have different energies and this difference in energy lifts the
degeneracy of the electron spin states
• The energy difference is given by:
E=E+-E-=hv=gmBB
03-03-02: LINE WIDTH OF ESR SIGNAL

The line width of ESR resonance depends on the relaxation time of the spin state under
study. Out of the two possible relaxation processes, the spin -spin relaxation is very
efficient, unless the sample is extremely dilute. The spin -spin relaxation time comes out to
be 10–6 to 10–8 s, much shorter than the spin-spin relaxation time in case of NMR. The
spin lattice relaxation is efficient at room temperature giving relaxation time of about 10 –
6s, but becomes progressively less efficient at reduced t emperatures. For most samples,
therefore we can choose 10–7s as a typical relaxation time and, using this in Heisenberg’s
relation.
An even shorter relaxation time will increase this width, and line width of 10 MHz is not
uncommon. Clearly, it is a much wider spectral line, than in case of NMR, where we find a
normal line width for a liquid to be some 0.1 Hz
A broad line is more difficult to observe and measure than a sharp line and, for this reason
the ESR signals are recorded as the derivative of the ab sorption curve with respect to the
magnetic field. An ESR absorption peak and its first derivative with respect to the magnetic
field are shown in Fig. 6.4(a) and Fig. 6.4 (b) respectively.

INTENSITY OF ESR SIGNALS:
The energy separation between the two spin states of an electron is much more than the
energy separation between two nuclear spin states. The relative population of electrons in
lower and higher energy spin states is governed by the Boltzman’s distribution law :
Thus, the lower energy spin state is more populated than the upper energy spin state of the
electron. The difference in population between two electronic spin states is larger E in the
former case.  than that betw een tw o nuclear spin states due to the large value of
Consequently, the ESR signals are expected to be more intense than the NMR signals.
INSTRUMENTAL TECHNIQUE IN ESR SPECTROSCOPY:
The ESR spectrum like that of NMR can be recorded in two ways. One can either ) across
resonance keeping the magnetic field (BZ) constant or t hevary the frequency (magnetic
field is varied keeping the frequency constant. The latter way is usually preferred since it is
easier to very the magnetic field keeping the stability at very high levels. In ESR
Experiment, it is the magnetic component of the electromagnetic radiation that interacts
with the magnetic dipole associated with the unpaired electron. If the oscillating magnetic
field vector of the radiation is parallel to the applied magnetic field, only an oscillation of
the energy level occurs and not a reorientation of the electron magnetic moment. Transition
between the levels will take place only when there is a reorientation of the electron
magnetic moment. Thus, for successful ESR absorption, the oscillating magnetic field of
the radiation must be perpendicular to the applied magnetic field.
The basic components of a X-band ESR spectrometer are:
a. An electromagnet capable of supplying a homogenous magnetic field which can be
varied linearly on either side of the magnetic field. (b) Source of microwave
radiation in the frequency region of 9.5 GHz. (c) A suitable sample cavity. (d)
Arrangements for transmitting the radiation energy into the sample cavity. (e)
Detection system to measure the variation in microwave power. (f) A suitable
oscilloscope or recorder.

A simple block diagram of a balanced bridge ESR spectrometer is given in Fig. 6.5
The usual source of microwave radiation is a klysteron oscillator which produces
monochromatic radiation of required frequency. The radiation from the sourc e is
transmitted to the sample cavity through a microwave impedance bridge. The rectangular
Microwave cavity which contains the sample is kept in between the pole pieces of the
electromagnet. A dummy load is kept in the third arm and a semiconducting cryst al in the
fourth arm of the microwave bridge. The radiations that arrive in the fourth arm are
detected by the crystal. It is then amplified and fed to a suitable recorder. Phase sensitive
detectors are usually used to detect ESR signals which are represen ted as absorption or first
derivative curves. The magnetic field is swept over a small range across the resonance
condition by varying the current in a pair of sweep coils mounted on the cavity walls.
When the bridge is in a balanced position, microwave po wer flows only in two arms - the
one to the cavity (arm -2) and the other to the dummy load (arm 3). There will not be any
power in the 4th arm. Power in the 4th arm will be there only when the bridge is not
balanced. Thus, if the balance exists, initially no signal appears at the detector and when
the sample absorbs, the balancing of bridge is lost and power appears in the 4th arm
resulting in ESR signals. The width of ESR signals is farely large and hence the spectrum is
usually recorded in the first derivative form which enables us to fix up the frequency
position and estimate the intensity more precisely. Another advantage of derivative from is
that it gives a well defined line width.

SOLVED PROBLEMS 02
190) Which of the following electromagnetic radiation is used in ESR?
(A) IR radiation
(B) Radio waves
(C) X-radiation
(D) Microwaves
191) For an unbound electron, value of Lande’ factor (g-factor) will be equal to
(A) 1.0098
(B) 2.0023
C) 3.0015
(D) 6.0621
192) What is Hyperfine Splitting?
The ESR signal is due to transition of electrons from the spin state ms = -l/2 to
the spin state ms = +1/2. — spin flip
• This spin state may interact with magnetic moment of nuclei, with which the
unpaired electron may be partially or wholly associated.‘This interaction may
lead to splitting of resonance signals in to several lines. This is Hyperfine
splitting.
193) How many ESR spectral lines are observed if an unpaired electron, delocalised on two
non-equivalent protons, is placed in magnetic field?
Ans-In the presence.of a magnetic field the unpaired electron will have
two energy levels giving rise to a single ESR fine. This line will split
further into a doublet due to the first proton I = ½. This doublet will
further split into two doublets ( due to second pro ton, because each proton
has different hyperfine splitting constant. With selection rules ^m, = 0,
four lines will be observed in the ESR spectrum.
03-03-03: HYPERFINE STRUCTURES

The interaction of magnetic moment of an unpaired electron with those of nei ghboring
magnetically active nuclei results in the splitting of ESR signals into (2nI+1) components,
where n and I are the number and nuclear spin respectively of magnetic nuclei. This
splitting of ESR signals under the influence of neigbbouring magnetical ly active nuclei
results in hyperfine structures of ESR signals.
The energy of interaction between the magnetic moment of unpaired electron and that of a
magnetic nucleus depends upon the direction of the magnetic moment of the electron
relative to that of the magnetic nucleus. The interaction energy is expressed as am Sm I ,,
where ‘a’ is a constant, called hyperfine coupling constant or hyperfine splitting constant. It
is a measure of the extent of interaction between the magnetic moment of the electron a nd
that of the interacting magnetic nucleus. Now, the energies of the electronic spin states
under the influence of a nearby magnetic nucleus is given by

Thus, for a given value of mS, the energy of electronic spin state also depends upon the
value of mI .
ESR SPECTRUM OF HYDROGEN ATOM:

SELECTION RULE FOR ESR:

ESR SPECTRUM OF ONE ELECTRON SYSTEM COUPLED TO A NUCLEUS OF SPIN, I
= 1:
The energy levels and allowed transitions for an electron spin coupled to a nucleus of spin,
I =1, are shown in Fig. 6.8
Three transitions of equal intensity, with separation equal to hyperfine coupling constant (a)
are expected. Their energies are:

ESR SPECTRUM DUE TO AN UNPAIRED ELECTRON COUPLED TO TWO MAGNETIC
NUCLEI:
The energy of spin states of an unpaired electron coupled to two magnetic nuclei are given
by

Here three conditions may arise, based on the relative magnitudes of a1 and a2.
The second peak will be twice as intense as the other two peaks, i.e., their intensity ratio
will be 1 : 2 : 1. The interaction of an unpaired electron with two identical protons (a1 = a2)
with allowed ESR transitions is shown in Fig. 6.10.

SOLVED PROBLEMS 03
194) Magnetic field strength of 0.1 Tesla is equal to
A) 10 Gauss
(B) 100 Gauss
(C) 1000 Gauss
(D) 10000 Gauss
15
195) An adjacent atom of N can split the spectral lines of electron in to
(A) 2
(B) 3
(C) 4
(D) 5
196) An ESR spectrum shows only three lines. Explain how it could arise from: (a)
Hyperfine coupling to two nuclei with spin = 1/2 (b) Hyperfine coupling to a nucleus
with spin = 1
(a) For two equivalent nuclei (I = 1/2) gives the total I = 1; so (2nI+ 1)
rule gives 2×1×1+1 = 3 lines, with an intensity distribution of 1: 2:1. (b)
In case we have a nucleus with spin I = 1; then by using 2 nI + 1, we get
2x 1x1+1 = 3 lines in the spectrum. These lines will be of equal intensity.
197) What is zero field splitting? Explain with suitable example.
198) Describe the experimental technique for recording ESR spectrum.
199) What is Magnet System?
The resonant cavity is placed between the poles pieces of an
electromagnet.

The field should be stable and uniform over the sample volume.
The stability of field is achieved by energizing the magnet with a highly
regulated power supply.
The ESR spectrum is recorded by slowly varying the magnetic field
through the resonance condense by sweeping the current supplied to the
magnet by the power supply.
03-03-04: ZERO FIELD SPLITTING AND FINE STRUCTURE

When a metal ion is placed in a crystal field, the degeneracy of d -orbitals is lifted by the
electrostatic interactions, but the spin degeneracy remains, until a magnetic field is applied.
However, when the species contains more than one unpaired electrons, the spin degenracy
can also be destroyed by the crystal field. Thus, the spin levels may be split even in the
absence of a magnetic field. This phenomenon is called zero field splitting. For species
with an odd number of unpaired electrons, the spin degeneracy of every level remains
doubly degenerate. This is known as Kramer’s degeneracy. For an even number of unpaired
electrons, the spin degeneracy may be removed completely by the crystal field.
Let us consider the case of a molecule or ion with two unpaired electrons, giving rise to a
total spin of S=1. The two unpaired electrons per molecule or ion forming the triplet state
can be treated for most ESR purposes as a single particle with spin 1. Thus, the angular
momentum vector corresponding to S = 1 is given by :
In the absence of a magnetic field, this vector orients itsel f randomly in space. When a
magnetic field is applied, the vector can take up one of the three directions only -with,
across or against the field direction. The components of the angular momentum vector in
the direction of the applied field (BZ) are ms =+1 ,0 and -1. In the applied field, the ms =
+1state is raised in energy, the ms = –1 state is lowered and ms = 0 state remains unaffected
(Fig.6.16).

Applying the selection rule for spin allowed transitions, ms = ±1, only two transitions, ms
=–t to ms = 0 and ms = 0 to ms = +1 are allowed, but both will have identical energy and
hence give rise to only one spectral line. In fact, two spectral lines of different energy are
invariably observed.
Reason for the unsymmetrical splitting of spin energy levels giv ing rise to two spectral
lines :
Each state with S = 1 is made up of two electrons with parallel spins. We know that each
spin produces a small magnetic field in the vicinity of the other affecting the net field
experienced by its neighbour (dipolar spin s pin coupling). Thus, both spins in ms = +1 state
feel an applied field greater than the external field BZ and this state is raised in energy. For
ms =–1, both feel a smaller field, which again raises their energy. In the case of ms =0, the
dipolar field is across the main applied field, hence it is neither raised nor lowered in
energy. Thus, the ms =0 state remains unaffected by the dipolar spin spin coupling.
The net effect of spin spin dipolar interaction is , then to raise both the ms = +1 and ms = –1
states with respect to ms = 0 state. Thus, the degeneracy of spin state is lifted due to spin
spin dipolar interactions, even in the absence of applied magnetic field. This splitting of
spin states in the absence of applied magnetic field is called zero field splitting (Fig. 6.17).
When a steadily increasing magnetic field is applied, the ms = ±1 levels diverge, the ms =
+1 level is raised in energy while ms = –1 level is lowered (Fig. 6.18)

It is clear that there will be transitions at two different appli ed fields and the spectrum will
consists of two fine structure lines.
LANDE SPLITTING FACTOR (G) OR, ELECTRON G-FACTOR:
Electron g-factor is the ratio of magnetic moment of the electron to the total spin angular
momentum of the electron. For a free electron the value of g is 2.0023. In many free
radicals, the value of the odd electron is close to that of a free electron, but in metal ions g
values are often quite different from the free electron value.
FACTORS AFFECTING g VALUES:
The value of g for an unpaired electron in gaseous atom/molecule/ion for which Russel
Saunders coupling (L-S coupling) is applicable, is given by the expression

Experimental value. No such agreement is found, however, when the unpaired electron is
placed in a chemical environment, either in a free radical, or in a transition metal ion
complex crystal lattice. In such a chemical environment, the orbital motion of the electron
is strongly perturbed and the orbital degenracy is partly removed or quenched. Jahn Teller
distortions also serve to lift the orbital degenracy. On the other hand, a certain amount of
orbital degenracy tends to be sustained as the result of spin orbit coupling. Thus, complete
removal of orbital degeneracy is prevented by spin orbit coupling but higher fold
degeneracies are often decreased by this effect. Thus, if an electron has orbital angular
momentum, this is maintained by coupling to the spin angular moment, and if it has a spin
angular momentum, this tends to generate orbital angular momentum. Consequently,
because of the quenching and sustaining competition, the orbital degeracy is partly but not
completely removed and a net orbital magnetic moment results, giving rise to a g value
different from the value 2.0023 expected if the orbital degeneracy were com pletely
removed. In most free radicals, the orbital contributions to the magnetic moment are very
small and the g values are nearly equal to free electron value of 2.0023. The small
deviations (±0.05) often observed for most free radicals are accounted for by the mixing of
low lying excited states with the ground state.
The properties of transition metals are determined to a large extent by the relative
magnitudes of the crystal field and spin-orbit coupling. These two interactions have
opposite effects on orbital degeneracy. Here three cases may be distinguished:
i. The effect of spin-orbit coupling is much larger than that of the crystal field : The
rare earth ions fall in this class because the f -electrons are deep seated and well
shielded from the crystal field effects so that the spin orbit coupling is not disturbed.
So, g values calculated using Eq. (6.12) for rare earth ions are in good agreement
with experimental values.
ii. The effect of crystal field is strong enough to destroy the spin -orbit coupling: The
first row transition metals fall in this category. The orbital degeneracy is no removed
completely because of the effect of some spin -orbit coupling. Consequently, a net

orbital magnetic moment results, giving rise to a g value different from the free
electron value. However, g value is closer to the free electron value of 2.0023 than
predicted from Eq. (6.12). Ions having an orbitally non -degenerate ground state such
as Fe3+ (6S) and Mn2+ (6S) have g values nearly equal to the free electron value,
since practically there is no orbital angular momentum. The slight deviation from the
free electron value is due to small spin orbit coupling.
iii. The effect of crystal field is strong enough to destroy the spin-orbit coupling
completely: This corresponds to covalent bonding and is applicable to the complexes
of 4d and 5d tansition metals and to the strong field complexes of 3d transition
metals such as cyanides.
200) What do you mean by hyperfine structure? How do they arise in ESR spectra?
201) Why is the line width of ESR signal larger than that of NMR signal? Why is ESR
signal presented in derivative form?
CHECK POINT 03-03
1) Unit for measurement of hyperfine splitting constant in ESR is
2) Hyperfine splitting that can be observed with two equivalent p rotons will be
3) As operating frequency increases, hyperfine splitting constant
4) Primary standard used in ESR is
SUMMARY
To make the student acquainted with paramagnetic species such as free radicals, transition
metal ions, ions and molecules having odd numb er of electrons and their identification
using the technique of electron spin resonance (e.s.r.) spectroscopy. Among the large
number of systems having one or more unpaired electrons, i.e. paramagnetic system, the
most important ones are free radicals, transition metal ions, ions and molecules having odd
number of electrons.
KEY WORDS
Humic Substance, Humic Acid, Fumic Acid, Electron Spin Resonance Signal,Spin Probe.
REFERENCES
1. https://www.scribd.com/doc/175906208/Electron-Spin-Resonance-It-s-Principles-and-
Applications
2. https://www.slideshare.net/MariyaRaju/electron-spin-resonance-spectroscopy-76805305
3. https://en.wikipedia.org/wiki/Electron_paramagnetic_resonance
4. https://www.jeol.co.jp/en/products/esr/basics.html
5. https://www.slideshare.net/kamleshpatade7/electron-spin-resonance-spectrometry
6. http://www.life.illinois.edu/crofts/pdf_files/Dikanov_Crofts_EPR_review_Chapter -3-
2006.pdf

1) Guass
2) 3

3) Remains constant
4) 1,1-diphenyl-2’-picrylhydrazyl
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=23ngD7piyBw
https://www.youtube.com/watch?v=DgA3-UnpSuI
WIKIPEDIA
https://en.wikipedia.org/wiki/Electron_paramagnetic_resonance
https://byjusexamprep.com/esr-full-form-i
OER
____
REFERENCE BOOKS
1. Fundamentals of molecular spectroscopy: C.N. Banwell and E.M. Mc Cash, 4th Edition,
Tata McGrow-Hill.
2. Physical methods in inorganic chemistry : R.S. Drago, Affiliated East west press private
limited, New Delhi
3. Molecular structure and spectroscopy: G. Aruldhas, Prentice Hall of India Private
limited, New Delhi.
4. A textbook of physical chemistry (Vol. -4) : K.L. Kapoor, Mac Millan India Limited

CREDIT 03-UNIT 04: IDENTIFICATION OF FREE RADICALS
LEARNING OBJECTIVES
 To know what are free radicals.
 To Learn about their structure
 To Known how radicals are generated
 To learn the reactivity of radicals.
INTRODUCTION
The full form of ESR is Electron Spin Resonance Spectroscopy. It is a branch of absorption
spectroscopy in which radiation having a frequency in the microwave region is absorbed by
the paramagnetic substances to induce a transition between the magnetic energy levels of
electrons with unpaired spins. Mаgnetiс energy sрlitting is dоne by аррlying а stаtiс
mаgnetiс field. Absorption spectroscopies operate at microwave fr equency 10 4 -10 6 MHz.
03-04-01: ESR SPECTRUM OF METHYL FREE RADICAL ( • CH3 )

In methyl free radical, an unpaired electron interacts with three equivalent protons.

Since the observed spectrum is symmetrical, the proton hyperfine couling constant is
isotropic and the unpaired electron density is distributed equally among the

:
Benzene anion can be formed by the reaction of an alkali metal with benzene in a solvent
such as tetrahydrofuran (THF). Benzene anion results when the alkali metal atom.
HYPERFINE SPLITTING RULES FOR PREDICTING THE NATURE OF ESR

SPECTRUM FOR MORE THAN ONE MAGNETIC NUCLEI:

SOLVED PROBLEMS 01
Author should provide here about 2-3 solved problems, on this Unit topics.
202)

Thus, four peaks are observed in the ESR spect rum of sodium atom.
203) The ratio of peak splitting that can observed with three equivalent protons will be
(A) 1:1
(B) 1:2:1
(C) 1:3:1
(D) 1:3:3:1

204) What is zero field splitting? Explain with suitable example

205) Why radio frequency is used in ESR?
The ESR linewidth is mainly due to spin-spin interactions between
electrons, which are independent of the magnetic field B. Therefore, at
radio frequencies, the ESR line is quite broad. It is therefore commonly
used as a g-marker to calibrate ESR spectrometers .
03-04-02: SOME APPLICATIONS OF ESR SPECTRAL STUDIES

The study of ESR spectrum has wide applications as given by the following examples:
i. Study of Free Radicals: Free radicals can be studied by ESR spectroscopy even in
small concentrations. The hyperfine structure of the ESR spectrum is a kind of
fingerprint that helps to identify the radical present in a sample. Besides using
nuclear hyperfine splitting to explain the number of magnetic nuclei present nearby
the unpaired electroli as discussed in Sec. 11.5, it can also help in mapping the
unpaired spin density. This can be done by using McComell Equation as given below:
Here a is the observed hyperfine splitting constant, Q is the hyperfine

splitting constant (or coupling constant) for unit density and p is the
electron density.

SOLVED PROBLEMS 02
206) Which of the following is a network solid? i) H2 O (ice) ii) SO2 (solid) iii) diamond
iv) I2
207) The lattice site in a pure crystal cannot be occupied by i) ion ii) electron iii) molecule
iv) atom
208) What is free radical?
Chemical species having one or more unpaired electrons are called free radicals. Homolytic
bond fission leads to the formation of free radicals. The free radicals are odd electron
molecules and are highly reactive. Free radicals are paramagnetic in that they possess a small
permanent magnetic moment due to the presence of unpaired electrons. This property is used
for the detection of the presence of free radicals.A notable example of a radical is the
hydroxyl radical, a molecule that has one unpaired electron on the oxygen atom. The two
other examples are triplet oxygen and triplet carbene (:C H2) which have two unpaired
electrons
209) Which Types of free radicals?
Neutral radical: These free radicals do not c harge them that’s why they have a much
lesser reactivity than the charged free radicals. Atoms have unpaired electrons if they
have an odd number of electrons. It can be electrically neutral because there are as
many as protons, so the net charge is zero.Cation radical: A radical cation is a
positively charged species that has an atom bearing an unpaired electron. Anion
radical: Radical anion is a subset of charged free radical species that carry a negative
charge. Radical anions are encountered in organic chemistry as reduced derivatives of
polycyclic aromatic compounds. For example, sodium naphthene.
CHECK POINT 03-04

1) The empty space left in hcp in three-dimensions is
2) (a) 52.4% (b) 80% (c) 26% (d) 74% Ans: (c)
3) In closed packed lattice containing n particles, the number of tetrahedral and
octahedral voids are
4) (a). 2n, n (b). n, n (c). n,2n (d). 2n ,n/2 Ans: (a)
5) Molecular solids have
6) (a) Very low melting points (b) Very high melting points (c) fairly low melting
points (d) None of these Ans: (c)
7) Among the following, the strongest bond is the
8) (a) hydrogen bond (b) metallic bond (c) covalent bond (d) Ionic bond Ans: (d)
SUMMARY
ESR transitions occur in the microwave region of the electromagnetic spectrum and are
accompanied by a change in the spin of t he unpaired electron.
ESR spectra are recorded as derivative curves.

The coupling of the electron and nuclear spins results in nuclear hyperfine interaction. This
results in the splitting of ESR line. The splitting is denoted by the hyperfine splitting
constant, a. The splitting pattern helps in the determination of structure of the free radical.
The g-factor for the electron is a universal constant and has the value g = 2.00232. The
deviation from this g value indicates the departure from free radical beha viour
(delocalisation).
KEY WORDS
____
REFERENCES
7. https://www.scribd.com/doc/175906208/Electron-Spin-Resonance-It-s-Principles-and-
Applications
8. https://www.slideshare.net/MariyaRaju/electron-spin-resonance-spectroscopy-76805305
9. https://en.wikipedia.org/wiki/Electron_paramagnetic_resonance
10. https://www.jeol.co.jp/en/products/esr/basics.html
11. https://www.slideshare.net/kamleshpatade7/electron -spin-resonance-spectrometry
12. http://www.life.illinois.edu/crofts/pdf_files/Dikanov_Crofts_EPR_review_Chapter -3-
2006.pdf
1) c
2) a
3) c
4) d
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=w9RAULFkqKQ
https://www.youtube.com/watch?v=n6JhsN0XYIU
WIKIPEDIA
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4310837/
https://copper.org/resources/properties/compounds/
OER
____
REFERENCE BOOKS
1. Fundamentals of molecular spectroscopy : C.N. Banwell and E.M. Mc Cash, 4th
Edition, Tata McGrow-Hill.
2. Physical methods in inorganic chemistry : R.S. Drago, Affiliated East west press
private limited, New Delhi
3. Molecular structure and spectroscopy : G. Aruldhas, Prentice Hall of India Private
limited, New Delhi.
4. A textbook of physical chemistry (Vol. -4) : K.L. Kapoor, Mac Millan India Limited

C REDIT 04

CREDIT 04-UNIT 01: ATOMIC ABSORPTION SPECTROSCOPY
LEARNING OBJECTIVES
 State the significance of Atomic Absorption Spectroscopy
 State basic principle and methodology of Atomic Absorption Spectroscopy
 Explain the types and application of Atomic Absorption Spectroscopy
INTRODUCTION
The science of atomic spectroscopy has yielded three techniques for analytical use: atomic
emission, atomic absorption, and atomic fluorescence. In order to understand the
relationship of these techniques to each other, it is necessary to have an understanding of
the atom itself and of the atomic process involved in each technique.
The electrons occupy orbital positions in an orderly and predictable way. The lowest
energy, most stable electronic configuration of an atom, known as the ‘‘ground state’’, is
the normal orbital configuration for an atom. If energy of the right magnitude is applied to
an atom, the energy will be absorbed by the atom, and an outer electron will be promoted to
a less stable configuration or ‘‘excited state’’. As this state is unstable, the atom will
immediately and spontaneously return to its ground state configuration. The electron will
return to its initial, stable orbital position, and radiant energy equivalent to the amo unt of
energy initially absorbed in the excitation process will be emitted. The process is illustrated
in Figure 1-1. Note that in Step 1 of the process, the excitation is forced by supplying
energy. The decay process in Step 2, involving the emission of l ight, occurs spontaneously.

As the orbital configuration of a large atom may be complex, there are many electronic
transitions which can occur, each transition resulting in the emission of a characteristic
wavelength of light, as illustrated in Figure 1 -2.
If light of just the right wavelength impinges on a free, ground state atom, the atom may
absorb the light as it enters an excited state in a process known as atomic absorption. This
process is illustrated in Figure 1-3. Note the similarity between this illustration and the one
in Step 1 of Figure 1-1. The light which is the source of atom excitation in Figure 1 -3 is
simply a specific form of energy. The capability of an atom to absorb very specific
wavelengths of light is utilized in atomic absorption spectrophotometry.
Atomic absorption absorption spectroscopy (AA or AAS) is one of the commonest

instrumental methods for analyzing for metals and some metalloids.
04-01-01: ATOMIC ABSORPTION SPECTROSCOPY
1) BASIC PRINCIPLE: ATOMIC ABSORPTION SPECTROSCOPY (AAS) is an
analytical technique that measures the concentrations of elements. It makes use of the
absorption of light by these elements in order to measure their concentration.
-Atomic-absorption spectroscopy quantifies the absorption of ground s tate atoms in the
gaseous state.
-The atoms absorb ultraviolet or visible light and make transitions to higher electronic
energy levels. The analyte concentration is determined from the amount of absorption.
- Concentration measurements are usually determined from a working curve after
calibrating the instrument with standards of known concentration.
-Atomic absorption is a very common technique for detecting metals and metalloids in
environmental samples.

ATOMIC ABSORPTION PROCESS: The quantity of interest in atomic absorption
measurements is the amount of light at the resonant wavelength which is absorbed as
the light passes through a cloud of atoms. As the number of atoms in the light path
increases, the amount of light absorbed increases in a predictable way. By measuring
the amount of light absorbed, a quantitative determination of the amount of analyte
element present can be made. The use of special light sources and careful selection of
wavelength allow the specific quantitative determination of individual elem ents in the
presence of others.
The source lamp for atomic fluorescence is mounted at an angle to the rest of the
optical system, so that the light detector sees only the fluorescence in the flame and
not the light from the lamp itself. It is advantageous to maximize lamp intensity with
atomic fluorescence since sensitivity is directly related to the number of excited atoms
which is a function of the intensity of the exciting radiation.
Figure 1-4 illustrates how the three techniques just described are i mplemented. While
atomic absorption is the most widely applied of the three techniques and usually offers
several advantages over the other two, particular benefits may be gained with either
emission or fluorescence in special analytical situations. This i s especially true of
emission, which will be discussed in more detail in a later chapter.
SOLVED PROBLEMS 01
210) The plasma in ICP–AES consists of :
(A)Positive ions only
(B) Electrons only
(C) Neutral molecules only
(D) Electrons, positive ions and neutral molecules
211) Nebuliser is being used in plasma spectroscopy to _____
A) Spray liquid in the chamber
(B) Detect the emitted radiation
(C) Produce plasma

(D) Convert liquid to aerosol and generate plasma
212) What is the importance of atomic spectra?
Atomic spectroscopy mainly consists of three techniques: atomic absorption
spectroscopy, atomic emission spectroscopy and atomic fluorescence
spectroscopy. Among these three, atomic absorption and emission spectroscopy
are crucial in forensic science because they can detect even trace amounts of
elements in tiny quantities of a sample
213) Why do different elements have different spectra?
Different elements have different numbers of protons, numbers, and
arrangements of electrons, so they have different spectra. Differences in spectra
reflect the amount of energy absorbed or released by atoms as their electrons
move between energy levels. So that’s why every element has its unique
spectra.
04-01-02: QUANTITATIVE ANALYSIS BY ATOMIC ABSORPTION

The atomic absorption process is illustrated in Figure 1-5. Light at the resonance
wavelength of initial intensity, Io, is focused on the flame cell containing ground state
atoms. The initial light intensity is decreased by an amount determined by the atom
concentration in the flame cell. The light is then directed onto the detector where the
reduced intensity, I, is measured. The amount of light absorbed is determined by comparing
I to Io.
Several related terms are used to define the amount of light absorption whic h has taken
place. The ‘‘transmittance’’ is defined as the ratio of the final intensity to the initial
intensity.
T = I/Io
Transmittance is an indication of the fraction of initial light which passes through the flame
cell to fall on the detector. The ‘‘percent transmission’’ is simply the transmittance
expressed in percentage terms.
%T = 100 x I/Io
The ‘‘percent absorption’’ is the complement of percent transmission defining the
percentage of the initial light intensity which is absorbed in the flame.

%A = 100 - %T
These terms are easy to visualize on a physical basis. The fourth term, ‘‘absorbance’’, is
purely a mathematical quantity.
A = log (Io/I)
Absorbance is the most convenient term for characterizing light absorption in absorption
spectrophotometry, as this quantity follows a linear relationship with concentration. Beer’s
Law defines this relationship:
A = abc
where ‘‘A’’ is the absorbance; ‘‘a’’ is the absorption coefficient, a constant which is
characteristic of the absorbing species at a specific w avelength; ‘‘b’’ is the length of the
light path intercepted by the absorption species in the absorption cell; and ‘‘c’’ is the
concentration of the absorbing species. This equation simply states that the absorbance is
directly proportional to the concentration of the absorbing species for a given set of
instrumental conditions.
This directly proportional behavior between absorbance and concentration is observed in
atomic absorption. When the absorbances of standard solutions containing known
concentrations of analyte are measured and the absorbance data are plotted against
concentration, a calibration relationship similar to that in Figure 1 -6 is established. Over
the region where the Beer’s Law relationship is observed, the calibration yields a straight
line. As the concentration and absorbance increase, nonideal behavior in the absorption
process can cause a deviation from linearity, as shown.
After such a calibration is established, the absorbance of solutions of unknown

concentrations may be measured and the concentration determined from the calibration
curve. In modern instrumentation, the calibration can be made within the instrument to
provide a direct readout of unknown concentrations. Since the advent of microcomputers,
accurate calibration, even in the nonlinear region, is simple.

SOLVED PROBLEMS 02
214) The analysis of fluoride in presence of anions in water sample is done with
(A) Nephelometer
(B) Ion analyser
(C) Fluorimeter
(D) Turbidimeter
215) Which one of the following element is used in cryoscopy to obtain very low temperature ?
(A) C
(B) Li
(C) B

(D) He
216) What are the main differences between atomic emission and atomic absorption?
The critical difference between atomic absorption and emission is that atomic
absorption describes how atoms absorb specific wavelengths from
electromagnetic radiation. In contrast, atomic emission explains how atoms
emit particular wavelengths.
217) Why are some spectral lines brighter than others?
Some spectral lines look brighter than others because these bright lines show
that when electrons get excited, it jumps from higher energy levels to lower
energy levels. When the electron jumps from a higher orbit, the energy released
in the form of a photon will be more significant, and we will get a brighter line.
Thus in the hydrogen spectrum, some lines are brighter than others.
04-01-03: CHARACTERISTIC CONCENTRATION AND DETECTION

LIMITS
Characteristic concentration and detection limit are terms which describe instrument
performance characteristics for an analyte element. While both parameters depend on the
absorbance observed for the element, each defines a different performance specification,
and the information to be gained from each term is different.
Characteristic Concentration:
The ‘‘characteristic concentration’’ (sometimes called ‘‘sensitivity’’) is a convention for
defining the magnitude of the absorbance signal which will be produced by a given
concentration of analyte. For flame atomic absorption, this term is expressed as the
concentration of an element in milligrams per liter (mg/L) required to produce a 1%
absorption (0.0044 absorbance) signal.
As long as measurements are made in the linear working region, the characteristic
concentration of an element can be determined by reading the absorbance produced by a
known concentration of the element and using the above equation.
There are several practical reasons for wanting to know the value of the characteristic
concentration for an element. Knowing the expected characteristic concentratio n allows an
operator to determine if all instrumental conditions are optimized and if the instrument is
performing up to specifications by simply measuring the absorbance of a known
concentration and comparing the results to the expected value. A known cha racteristic
concentration value also allows one to predict the absorbance range which will be observed
from a known concentration range or to determine the concentration range which would
produce optimum absorbance levels.
Detection Limits:

It should be noted that, while the magnitude of the absorbance signal can be predicted from
the value given for characteristic concentration, no information is given on how small of an
absorbance signal can be measured. Therefore, it is not possible to predict the minimu m
measurable concentration from a known characteristic concentration value. To determine
this quantity, more information on the nature of the measured absorbance signal must be
considered.
The smallest measurable concentration of an element will be determi ned by the magnitude
of absorbance observed for the element (characteristic concentration) and the stability of
the absorbance signal. An unstable or ‘‘noisy’’ signal makes it more difficult to distinguish
small changes in observed absorbance which are due to small concentration differences,
from those random variations due to ‘‘baseline noise.’’ Figure 1 -7 illustrates the concept of
the effect of noise on the quantitation of small absorbance signals. Signal "A" and signal
"B" have the same magnitude.
However, the much lower variability ("noise") of signal "B" permits even smaller signals to
be detected. The sensitivity of the two signals is the same, but there is a real difference in
detection limits.
The term ‘‘detection limit’’ incorporates a consideration of both signal size and baseline
noise to give an indication of the lowest concentration of an element which can be
measured. The detection limit is defined by the IUPAC as the concentration which will give
an absorbance signal three times the magnitude of the baseline noise. The baseline noise
may be statistically quantitated typically by making 10 or more replicate measurements of
the baseline absorbance signal observed for an analytical blank, and determining the
standard deviation of the measurements. The detection limit is then defined as the
concentration which will produce an absorbance signal three times the standard deviation of
the blank.
Routine analytical measurements at the detection limit are difficult, due to the fact that, by
definition, noise makes up a significant percentage of the total measurable signal. By
definition, the precision obtained at detection limit levels is ± 33% RSD (relative standard
deviation) when a three standard deviation criterion is used. Therefore, while it is pos sible
to distinguish analyte concentrations at the detection limit from zero, for good precision it

is necessary to limit routine analytical work to concentrations higher than the detection
limit.
SOLVED PROBLEMS 03
218) The compartment which contains hollow cathode lamp is filled with _______ in atomic
absorption spectroscopy.
(A) Ar gas
(B) HCl gas
(C) HNO3 vapours
(D) Cl2 gas
219) Atomic emission spectroscopy is
(A) The measurement of intensity of emitted light at a particular
wavelength from the atoms that are exited thermally.
(B) The measurement of absorbance of emitted light at a particular wavelength
from the atoms that are exited thermally.
(C) The measurement of intensity of emitted light at a particular wavelength
from the atoms that are excited by monochromatic light.
(D) The measurement of intensity of absorbed light at a particular wavelength
from the atoms that are exited thermally.
220) What are the uses of atomic spectroscopy?
Atomic Spectroscopy is used to identify the spectral lines of materials used in
metallurgy.Atomic Spectroscopy is used in pharmaceutical industries to find
traces of materials used.It is also used to study multidimensional elements.
221) Describe the types of atomic spectroscopy.
Atomic spectroscopy is classified into three main types, and they are,
a. Atomic emission spectroscopy: Atomic emission spectroscopy involves
energy transfer from the ground state to an excited state. The electronic
transition can be explained by atomic emission.
b. Atomic absorption spectroscopy: For absorption to occur, there should be
identical energy differences between the lower and higher energy levels.
According to the atomic absorption spectroscopy principle, free electrons
generated in an atomizer can absorb radiation at a specific frequency. It
measures the absorption of ground-state atoms in gaseous form.
c. Atomic fluorescence spectroscopy: Atomic fluorescence spectroscopy
combines atomic emission and atomic absorption because it involves excitation
and de-excitation radiation.
04-01-04: ATOMIC ABSORPTION INSTRUMENTATION

THE BASIC COMPONENTS:
To understand the workings of the atomic absorption spectrometer, let us build one, piece
by piece. Every absorption spectrometer must have components which fulfill the three basic
requirements shown in Figure 2-1. There must be: (1) a light source; (2) a sample cell; and
(3) a means of specific light measurement.

In atomic absorption, these functional areas are implemented by the components illustrated
in Figure 2-2. A light source which emits the sharp atomic lines of the element to be
determined is required. The most widely used source is the hollow cathode lamp. These
lamps are designed to emit the atomic spectrum of a particular element, and specific lamps
are selected for use depending on the element to be determined.
It is also required that the source radiation be modulated (switched on and off rapidly) to
provide a means of selectively amplifying light emitted from the source lamp and ignoring
emission from the sample cell. Source modulation can be accomplished with a rotating
chopper located between the source and the sample cell, or by pulsing the power to the
source.
Special considerations are also required for a sample cell for atomic absorption. An atomic
vapor must be generated in the light beam from the source. This is generally accomplished
by introducing the sample into a burner system or electrically heated furnace aligned in the
optical path of the spectrophotometer.
Several components are required for specific light measure ment. A monochromator is used
to disperse the various wavelengths of light which are emitted from the source and to
isolate the particular line of interest. The selection of a specific source and a particular
wavelength in that source is what allows the de termination of a selected element to be made
in the presence of others.
The wavelength of light which is isolated by the monochromator is directed onto the
detector, which serves as the ‘‘eye’’ of the instrument. This is normally a photomultiplier
tube, which produces an electrical current dependent on the light intensity. The electrical
current from the photomultiplier is then amplified and processed by the instrument
electronics to produce a signal which is a measure of the light attenuation occurring in the

sample cell. This signal can be further processed to produce an instrument readout directly
in concentration units.
LIGHT SOURCES:
An atom absorbs light at discrete wavelengths. In order to measure this narrow light
absorption with maximum sensitivity, it is necessary to use a line source, which emits the
specific wavelengths which can be absorbed by the atom. Narrow line sources not only
provide high sensitivity, but also make atomic absorption a very specific analytical
technique with few spectral interferences. The two most common line sources used in
atomic absorption are the ‘‘hollow cathode lamp’’ and the ‘‘electrodeless discharge lamp.’’
The Hollow Cathode Lamp:

The hollow cathode lamp is an excellent, bright line source for most of the elemen ts
determinable by atomic absorption. Figure 2 -3 shows how a hollow cathode lamp is

constructed. The cathode of the lamp frequently is a hollowed -out cylinder of the metal
whose spectrum is to be produced. The anode and cathode are sealed in a glass cylind er
normally filled with either neon or argon at low pressure. At the end of the glass cylinder is
a window transparent to the emitted radiation.

Instrumentation of Atomic Absorption Spectroscopy:
Atomizer In order for the sample to be analyzed, it must first be atomized. This is an
extremely important step in AAS because it determines the sensitivity of the reading. The
most effective atomizers create a large number of homogenous free atoms. There are many
types of atomizers, but only two are commonly used: flame and electrothermal atomizers.
Flame atomizer Flame atomizers (Figure ) are widely used for a multitude of reasons
including their simplicity, low cost, and long length of time that they have been utilized.
Flame atomizers accept an aerosol from a nebulizer into a flame that has enough energy to
both volatilize and atomize the sample.
When this happens, the sample is dried, vaporized, atomized, and ionized. Within this
category of atomizers, there are many subcategories determi ned by the chemical
composition of the flame. The composition of the flame is often determined based on the
sample being analyzed. The flame itself should meet several requirements including
sufficient energy, a long length, non-turbulent, and safe.
Figure: A schematic diagram of a flame atomizer showing the oxidizer inlet (1) and fuel
inlet (2)

Electrothermal atomizer:
Although electrothermal atomizers were developed before flame atomizers, they did not
become popular until more recently due to improveme nts made to the detection level. They
employ graphite tubes that increase temperature in a stepwise manner. Electrothermal
atomization first dries the sample and evaporates much of the solvent and impurities, then
atomizes the sample, and then rises it to an extremely high temperature to clean the
graphite tube. Some requirements for this form of atomization are the ability to maintain a
constant temperature during atomization, have rapid atomization, hold a large volume of
solution, and emit minimal radiation. Electrothermal atomization is much less harsh than
the method of flame atomization.
Radiation source:
The radiation source then irradiates the atomized sample. The sample absorbs some of the
radiation, and the rest passes through the spectrometer to a detector. Radiation sources can
be separated into two broad categories: line sources and continuum sources. Line sources

excite the analyte and thus emit its own line spectrum. Hollow cathode lamps and
electrodeless discharge lamps are the most commonly used examples of line sources. On the
other hand, continuum sources have radiation that spreads out over a wider range of
wavelengths. These sources are typically only used for background correction. Deuterium
lamps and halogen lamps are often used for this purpose.
Spectrometer:
Spectrometers are used to separate the different wavelengths of light before they pass to the
detector. The spectrometer used in AAS can be either single -beam or double-beam.
Singlebeam spectrometers only require radiation that pa sses directly through the atomized
sample, while double-beam spectrometers (Figure 1.4.121.4.12), as implied by the name,
require two beams of light; one that passes directly through the sample, and one that does
not pass through the sample at all. (Insert diagrams) The single-beam spectrometers have
less optical components and therefore suffer less radiation loss. Double -beam
monochromators have more optical components, but they are also more stable over time
because they can compensate for changes more re adily.
Control of Analytical Interferences:

Matrix Interference:
The first place in the flame atomization process subject to interference is the very first step,
the nebulization. If the sample is more viscous or has considerably different surface tension
characteristics than the standard, the sample uptake rate or nebulization efficiency may be
different between sample and standard. If samples and standards are not introduced into the
process at the same rate, it is obvious that the number of atoms in the light beam and,
therefore, the absorbance, will not correlate between the two. Thus, a matrix interference
will exist.
An example of this type of interference is the effect of acid concentration on absorbance.
From Figure 3-2, it can be seen that as phosphoric acid concentration increases (and the
sample viscosity increases), the sample introduction rate and the sample absorbance
decrease. Increased acid or dissolved solids concentration normally will lead to a negative
error if not recognized and corrected. Matrix interferences can also cause positive error.
The presence of an organic solvent in a sample will produce an enhanced nebulization
efficiency, resulting in an increased absorption. One way of compensating for this type of
interference is to match as closely as possible the major matrix components of the standard
to those of the sample. Any acid or other reagent added to the sample during preparation
should also be added to the standards and blank in similar concentrations.

Chemical Interference:
A second place where interference can enter into the flame process is in step number 5 of
Figure 3-1, the atomization process. In this step, sufficient energy must be available to
dissociate the molecular form of the analyte to create free atoms. If the sa mple contains a
component which forms a thermally stable compound with the analyte that is not
completely decomposed by the energy available in the flame, a chemical interference will
exist.
The effect of phosphate on calcium, illustrated in Figure 3 -4, is an example of a chemical
interference. Calcium phosphate does not totally dissociate in an airacetylene flame.
Therefore, as phosphate concentration is increased, the absorbance due to calcium atoms
decreases.
There are two means of dealing with this problem. One is to eliminate the interference by
adding an excess of another element or compound which will also form a thermally stable
compound with the interferent. In the case of calcium, lanthanum is added to tie up the
phosphate and allow the calcium to be atomized, making the calcium absorbance
independent of the amount of phosphate. There is a second approach to solving the
chemical interference problem. Since the problem arises because of insufficient energy to
decompose a thermally stable analyte compound, the problem can be eliminated by
increasing the amount of energy; that is, by using a hotter flame. The nitrous oxide -
acetylene flame is considerably hotter than air-acetylene and can often be used to minimize
chemical interferences for elements generally determined with air-acetylene. The phosphate
interference on calcium, for instance, is not observed with a nitrous oxide -acetylene flame,
eliminating the need for the addition of lanthanum.

Ionization Interference:
There is a third major interference, however, which is often encountered in hot flames. As
illustrated in Figure 3-1, the dissociation process does not necessarily stop at the ground
state atom. If additional energy is applied, the ground state atom can be thermally raised to
the excited state or an electron may be totally removed from the atom, creating an ion. As
these electronic rearrangements deplete the number of ground state atoms available for light
absorption, atomic absorption at the resonance wavelength is reduced. When an excess of
energy reduces the population of ground state atoms, an ionization interference exists.
Ionization interferences are most common with the hotter nitrous oxide -acetylene flame. In
an air-acetylene flame, ionization interferences are normally encountered only with the
more easily ionized elements, notably the alkali metals and alkaline earths.
Ionization interference can be eliminated by adding an excess of an element which is very

easily ionized, creating a large number of free electrons in the flame and suppressing the
ionization of the analyte. Potassium, rubidium, and cesium salts are commonly used as
ionization suppressants. Figure 3-5 shows ionization suppression for the determination of
barium in a nitrous oxideacetylene flame. The increase in absor ption at the barium
resonance line, and the corresponding decrease in absorption at the barium ion line as a
function of added potassium, illustrate the enhancement of the ground state species as the
ion form is suppressed. By adding 1000 mg/L to 5000 mg/L potassium to all blanks,
standards and samples, the effects of ionization can usually be eliminated.

SPECTRAL INTERFERENCES:
Spectral interferences are those in which the measured light absorption is erroneously high
due to absorption by a species other than the analyte element. The most common type of
spectral interference in atomic absorption is ‘‘background absorption.’’
Background Absorption: Background absorption arises from the fact that not all of the
matrix materials in a sample are necessarily 100% atomized. Since atoms have extremely
narrow absorption lines, there are few problems involving interferences where one element
absorbs at the wavelength of another. Even when an absorbing wavelength of another
element falls within the spectral bandwidth used, no absorption can occur unless the light
source produces light at that wavelength, i.e., that element is also present in the light
source. However, undissociated molecular forms of matrix materials may have broadband
absorption spectra, and tiny solid particles in the flame may scatter light over a wide
wavelength region. When this type of nonspecific absorption overlaps the atomic absorption
wavelength of the analyte, background absorption occurs. To compensate for this problem,
the background absorption must be measured and subtracted from the total measured
absorption to determine the true atomic absorption component.
While now virtually obsolete, an early method of manual background correction illustrates
clearly the nature of the problem. With the ‘‘two line method’’, background absorption,
which usually varies gradually with wavelength, was independently measured by using a
nonabsorbing emission line very close to the atomic line for the analyte element, but far
enough away so that atomic absorption was not observed, as illustrated in Figure 3 -6. By
subtracting the absorbance measured at the nonabsorbing line from the absorbance at the
atomic line, the net atomic absorption was calculated. Nearby, nonabsorbing lines are not
always readily available, however, and inaccuracies in background correction will result if

the wavelength for background measurement is not extremely close to the resonance line.
Therefore, for accuracy, as well as convenience, a different method was needed
SOLVED PROBLEMS 04
222) In hollow cathode lamp of atomic absorption spectroscopy, the cathode is made up of /
coated with _______
A) Graphene
(B) multiwalled carbon nanotube
(C) carbon black
(D) same as analyte element of interest
223) In atomic emission spectroscopy the flame acts as
(i) Source of excitation;
(ii) Source of light;
(iii) source of vaporization;
(iv) Source of ionization
(A) (i) and (ii)
(B) (iii) and (ii)
(C) (ii) and (iv)
(D) (i) and (iii)
224) What are the dark lines in a spectrum?
When we observe any dark line in a spectrum, it corresponds to specific
wavelengths being missing due to absorption by the matter, which is in the
form of atoms or molecules on their way. So the dark line represents the
“absence of light” in a spectrum, not any particular wavelength (colour) of
light.
225) What is Application of ABS?
•Atomic absorption spectroscopy is one of the most widely used techniques for
the determination of metals at trace levels in solution.
•Its popularity as compared with that of flame emission is due to its relative
freedom from interferences by inter element effect and its relative insensitivity
to various in flame temperature.
• Only bor the routine determination of alkali and alkaline earth metals is flame

photometry usually preferred.
• Widely used for metal analysis in enviromental sample(air,water,and soil) and
in biological fluid and tissues.
CHECK POINT 04-01
1) In atomic absorption spectroscopy the most strongly absorbed light is called as
2) For some kind of analysis in atomic spectroscopy, nitrogen is allowed to flow over
the flame
3) The broadening of the spectral line in atomic emission spectroscopy may be due to
4) Releasing agents are used in atomic emission spectroscopy to prevent
SUMMARY
A colorimetric field method for the determination of As and Sb was compared with atomic absorption
(AA) techniques using both graphite furnace atomic absorption and the hydride generating technique
with the heated quartz cell.During the intercomparison experiments the importance of the addition of
KI before the addition of the NaBH4 reagent to the sample was clearly demonstrated. Compared with
the colorimetric technique the AA hydride technique with the heated quartz cell was found to suffer
from interferences by other hydride forming elements. Slow addition of NaBH4 (5 min in case of the
colorimetric method) results in a longer reaction time giving a complete transformation of the hydride
forming elements. The work also includes the optimization of various analytical parameters with
respect to the hydride technique.
KEY WORDS
Calcium, Magnesium, zinc,lubricating oils ,Atomic absorption Spectrscopy
REFERENCES
Adah CA, Abah J, Ubwa ST, Ekele S (2013). Soil availability and uptake of some heavy
metals by three staple vegetables commonly cultivated along the south bank of River
Benue, Makurdi, Nigeria. International Journal of Environment and Bioenergy 8:56 -67.
Agrawal J, Gupta N, Bharadwaj N, Kalpana S (2011). Determination of heavy metal
contents in samples of different medicinal plants. International Journal of C hemical Science
9(3):1126-1132.

1) Resonance line
2) To exclude atmospheric oxygen
3) Lorentz effect; quenching;
4) Anionic interference
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=Wap9pQEN4gE
https://www.youtube.com/watch?v=TB-Wt3p1UAU

WIKIPEDIA
https://en.wikipedia.org/wiki/Atomic_absorption_spectroscopy
https://www.academia.edu/33132406/ATOMIC_ABSORPTION_SPECTROSCOPY_Pri
nciple
OER
____
REFERENCE BOOKS
1. Deewan SK. Organic spectroscopy (N.M.R., I.R., Mass and UV).New Delhi:CBS
Publishers and Distributors Pvt. Ltd.; 2010.
2. William K. Organic Spectroscopy. Macmillan: Macmillan Chemistry Text; 1991.
3. Beckett AH, Stenlake JB. Practical Pharmaceutical Chemistry: Part -II. London:The
Athlone Press; 1988.
4. Verma RM, Analytical Chemistry:Theory and Practice. Third Edition. New Delhi: CBS
5. Ravi Sankar S., Text Book of Pharmaceutical Analysis, Tiruneliveli:Rx Publications:
2006.

CREDIT 04-UNIT 02: PLASMA SOURCES & APPLICATIONS OF
FLAME EMISSION SPECTROMETRY
LEARNING OBJECTIVES
 Explain the principle of flame photometry,
 Define atomic spectroscopic methods and classify them,
 Draw a schematic diagram illustrating different components of a flame photometer,
 Enlist the applications of flame photometry,
 State the merits and limitations of the flame photometric technique.
INTRODUCTION
Plasma source mass spectrometry (PS MS) has a longlasting, unbroken and still increasing
record of excellent performance. However, in most publications, MS automatically is
associated with a ‘soft’, low-temperature ion source, as though MS would exclusively be
performed by lowtemperature ion sources for organic molecular ion formation and
fragmentation. This is not justified, especially because the performance of PS MS is
undoubtedly superior in useful aspects of analytical chemistry. Inductively coupled plasma
(ICP) MS, the most widely applied PS MS, has played and is still playing an important role
in many fields of applied science and research. The complementarity of ICP MS with other
types of ion source MS (such as electrospray ionization MS) and the recent tremendous
progress made in the development of these for bioinorganic analytical chemistry have been
well documented in an excellent review. The information that can be recovered from the
application of the two types of ion sources is quite differ ent but ultimately complementary
(Table 1), which is affirmed by the efforts todevelop modulated ion sources capable of
generating either elemental ions or molecular fragment ions within the same ion source
device.
04-02-01: PRINCIPLES& INTRUMENTATION
PRINCIPLES: Inductively coupled plasma (ICP) mass spectrometry (MS) is routinely used
in many diverse research fields such as earth, environmental, life and forensic sciences and
in food, material, chemical, semiconductor and nuclear industries. The high ion density and

the high temperature in plasma provide an ideal atomizer and element ionizer for all types
of samples and matrices introduced by a variety of specialized devices. Outstanding
properties such as high sensitivity (ppt–ppq), relative salt tolerance, compound -independent
element response and highest quantitation accuracy lead to the unchallenged performance
of ICP MS in efficiently detecting, identifying and reliably quantifying trace elements. The
increasing availability of relevant reference compounds and high separatio n selectivity
extend the molecular identification capability of ICP MS hyphenated to species -specific
separation techniques. While molecular ion source MS is specialized in determining the
structure of unknown molecules, ICP MS is an efficient and highly s ensitive tool for target-
element orientated discoveries of relevant and unknown compounds.
P, Se natively binding metals (Zn, Fe, Mn, Cu, Ni, Mo, Cr) have been detected and
quantified by ICP MS, emphasizing its potential in life science research. Paralle l to
proteomics research, the activity in bioinorganic speciation has rendered metallomics
studies accessible, a new research field linked to proteomics, since more than 25% of all
proteins contain metals.
In the following, an overview is given on the spec ific role ICP MS plays in diverse research
fields. Special or unique features are highlighted through recently published examples,
rather than providing a complete review of the literature.
INTRUMENTATION:
1) ICP – A HIGH-TEMPERATURE ATOMIZING ION SOURCE: An ICP is the
standard high-temperature ion source used almost exclusively in commercial
instruments for PS MS.5 Details of such an ion source and its interface are given in
Fig. 1. It provides temperatures of approximately 5500 °Chat no material can
withstand. Thus, it is the most versatile atomizer and element ionizer available.
Contrary to low-temperature ion sources for molecular ions, in a plasma all bonds

are broken irrespective of their chemical bonding. Hence, the data acquired from a
plasma ion source corresponds to the total content of an element in the sample. The
elemental response is independent of the different species containing the same
element, enabling simple and accurate species -unspecific, multielement quantitation
based on commercially available certified multielement standards and certified
reference materials (CRMs).
6 Simple mass spectra in the mass-to-charge (m/z) range 5–250 are generated at the
expense of multiple fragmentations and the loss of information on molecular mass
and structure. Another unique property of a plasma is that it has the highest ion
density (ArC and e) and hence provides the highest collision rate available. In
combination with the high temperature, this drives the ionization of an element
toward the physical limits set by the ionization potential of the element. Thus, much
higher analyte ion densities and higher sensitivities are generated than by other ion
sources. Additionally, the ICP ion source is much less vulnerable to the salt and
solvent loads introduced by a sample and tolerates, for example, 100 mmol/l salt
concentrations. Salt and solvent tolerance restrictions, however, do exist, as these
can induce clogging of the cone and ultimately contaminate the instrument.
However, if the salts injected contain volatile elements that decompose in the
plasma into gaseous components, hundreds of millimoles per liter are tolerated and
no instrument contamination occurs. This is used to minimize the influence of the
variable sample matrix by adding a high level of vola tile acid (0.1–1 mol/l HNO3)
to the samples. Under such a regime, it is not surprising that sample matrix effects
are much less severe than in any other type of ion source. The known
matrixdependent response in ICP MS (acid effect, – space charge effects, general
effects from concomitant ions, organics on aerosol formation22) can be accounted
for by matrixadapted standards, standard addition to the matrix or isotope dilution.
These outstanding properties make ICP MS extremely useful, efficient and reliable
in detecting, keeping track of, identifying and quantifying elements. Even molecules
can be identified that contain at least one heteroatom if a reference compound is
available. In this case, the instrument has to be hyphenated to a species –specific
separation technique that has to provide sufficient selectivity to separate the
compound for identification and quantitation.
2) DIVERSE SAMPLE INTRODUCTION SYSTEMS MAKING ICP MS VERSATILE:
Contrary to large variations in mild ion sources (ESI, CI, FAB, etc.), in commercial
instruments there is no variation of the plasma ion source. However, in addition to
different types of nebulizers and desolvating systems, a large variety of sample
introduction systems have been developed for ICP MS. An overview of the basic
types of introduction systems is shown in Fig. 2. Liquid solution nebulization is by

far the most economical and most often used sample introduction technique. Many
solid samples have to be digested and dissolved to obtain a homogeneous sample.
For direct access to analytes in solids and on surfaces, laser ablation (LA) is used
with a spatial resolution on the micrometer scale (¾1 µm), which is ideally suited
for microsampling on surfaces and in-depth profile analysis. In several fields, it is
the preferred technique and in some cases the only avenue available. This is the case
for the analysis of rock inclusions in geology, tree rings and biological tissue
sections and for many other microsurface area samplings such as in material and
forensic sciences and for virtually nondestructing sampling on valuable antique and
archaeological objects. LA of proteins directly from sodium dodecyl sulfate
polyacrylamide electrophoresis (SDS-PAGE) gels after two-dimensional separation
has become of general interest for life science studies and was used to determine
metal distribution in a proteome, a methodology that has been recently improved.
Electrothermal vaporization (ETV) allows in situ sample preparation (drying,
decomposition of heat-labile matrix) and hence sample preconcentration. Higher
sample introduction efficiency is provided by highefficiency nebulizers, namely,
ultrasonic nebulizers (USN), LA and ETV. If available, no or low solvent -
introducing systems are preferred such as dried aerosols, LA and ETV, since the y
generate fewer polyatomic ions and lower background levels. LA, ETV and solution
nebulization have been compared for liquid samples, confirming enhanced
reproducibility but lower detection limits for solution nebulization.

3) SPECIES-INDEPENDENT TOTAL ELEMENT QUANTITATION BY ICP MS:
The capability of gathering chemical information and other outstanding features of
ICP MS are summarized in Table 2. Detecting and quantifying 85% of all elements
down to concentrations not measurable by other techniques opens a broad analytical
window, allowing a unique holistic approach. This means a true nontarget approach
that semiquantifies all detectable elements in a full mass scan, thereby discovering
problems more reliably than by preselecting some elements and excludin g the
unexpected ones. Both positive as well as negative findings are confirmed, which is
a fundamental prerequisite to completely assess all elementrelated quality and
compositional aspects of a sample. Besides this important aspect, ICP MS on its
own provides chemical information on a basic level, such as total single elemental
contents or elemental and isotope ratios. Here the technique has an outstanding
record as a highly sensitive, high-throughput and, over its total life cycle, a fairly
inexpensive analytical tool. When measuring on a routine basis dozens of
parameters in a sample and thousands of samples per year, the costs calculated per
parameter for an instrumental life cycle (¾10 years) is in the same order of
magnitude as the cost of a sample vial. This is an extremely good cost–benefit ratio
despite a somewhat higher material and running cost (Ar consumption).

To cover the whole mass range for all elements, a simple quadrupole mass analyzer
provides ample resolution (R D 300) to detect all the isotopes of an element
differing by 1 atomic mass unit (amu). This isotope -specific detection is element
specific, since each element has at least one isotope that differs from all others by 1
amu. Without preconcentration, detection limits are usually in the nanogram per liter
range and below when detecting with a highly sensitive, high -resolution ICP MS
instrument. In fact, the simple access to isotope quantitation is the most utile feature
of ICP MS. A large part of elements (80%) is composed of several isotopes.
Naturally occurring stable isotopes are routinely measured, as well as unstable
isotopes in nuclear research. Kinetically fractionated isotope ratios need higher -
precision ICP mass spectrometers that are provided with multicollector detection
units. Highly concentrated elements can be measured using their low -abundance
isotope(s) (less sensitive), thereby protecting the detector and increasing the
instrument flexibility to measure high and low concentrated elements in the same
run without diluting the samples. Furthermore, measuring at least two isotopes of
the same element allows not only safe element identification but also recognition of
the contributions from interfering masses by the deviation in natural isotopic ratios.
To deal with polyatomic interferences while reducing background levels, specialized
devices such as reaction/collision cells and high -resolution instruments have been
developed.
Sensitive single element determinations were very useful in many metal –protein
binding studies, e.g. revealing metals in enzymes and other protein-binding sites.
Very recently, the in vitro specific affinity of Cd to the estrogen binding site in the
estrogen receptor was demonstrated.38 A much more detailed picture is obtained by
determining multielement and multitraceelement compositions by ICP MS. It is a
well-established technique applied in many diverse fields such as envi ronmental
science, geology, pharmaceutical and biomedical sciences, bioinorganic analysis and
forensic investigations, among many others. Elemental compositions are used not

only to characterize and judge the quality aspects of a sample but are also often used
to diagnose processes or reveal the history of the sample. Multielement ratios are an
ideal tool to track processes or assign the provenance that leads to a particular
composition of a sample; e.g. the geographic production area can be assigned by the
elemental ratios in foodstuff and wine. Elemental cycling on a local or global scale
and element accumulation in living organisms can also be followed.
Isotope dilution experiments, that is, the addition of an enriched isotope of known
content to a sample, are increasingly used for different purpose. For quantitation it
is the most accurate method since an internal standard of ident ical chemical
behavior is measured. The direct determination of heteroelements or exchanging
these with enriched stable isotopes to tag molecules and proteins was established, as
well as analysis of conjugated and labeled proteins.50 Detection and, especia lly,
quantitation of such multiple elemental tags and labels by ICP MS are highly
advantageous in lifesciences. Particularly, the high sensitivity of this approach will
allow replacement of radioactive tracers by natural, stable isotopes. Isotope dilution
is also a very useful and elegant technique to investigate dynamic systems. The
content and kinetics of an element -exchanging pool, ranging in size from micro to a
large scale, can be determined by addition of enriched isotopes. For example,
enriched 207Pb was used to determine the Pb availability in contaminated soils.
Administration of isotope-enriched micronutrients and their dilution and
quantitation after passage through the body is a common method in nutrition
research to elucidate the uptake of minerals and nutritional mineral status.
4) ICP MS HYPHENATED TO SEPARATION TECHNIQUES FOR SPECIES -
SPECIFIC DETECTION AND IDENTIFICATION:
The high salt or acid tolerance of the plasma makes ICP MS an ideal elemental
detector for species-specific, highperformance separations techniques such as GC,
HPLC and CE (Fig. 3). ICP MS serves as a versatile and sensitive detector for
compounds containing known or unidentified heteroelements including metals and
nonmetals. The effluent of liquid chromatography is connected to a nebulizer to
introduce the effluent as an aerosol into the plasma. Such hyphenated systems built
for elemental speciation analysis are again used in many applied research fields.
Depending on the separation window, a partial elemental distribution finger print or
a complete elemental distribution for different compounds is obtained. The total
content of an element determined before separation allows calculation of the portion
missed by the separation technique used and the percentage of the individual peak
recovered compared to the total amount (Fig. 4). It is a unique and outstanding
advantage of ICP MS to easily provide quantitative control on elemental distribution
on each step of an experiment. Under such quantitative control, only relevant

unknown species are subsequently investigated by a molecular ion source MS for
detailed structural assignment. Such an approach has been beneficial in many cases,
and is typically chosen for discovering unknown compounds and studying metal –
protein interactions by elemental speciation analysis.8 A good example of this was
given in a recently published investigation in which the higher Cd tolerance among
plants was correlated for the
first time with the structural differences in phytochelatins (PC) complexing Cd and
thereby reducing its toxic effects. Cd–PC extracted from cells have been separated
by size exclusion (SE) and detected online by ICP MS. Cd -containing PC fractions
were further analyzed by ESI ToF MS, revealing an additional cysteine that allowed
the binding of more Cd and hence having a higher Cd tolerance. There is also a
growing interest in identification and characterization of natural selenium -
containing compounds since these have been demonstrated to inhibit tumor growth.
Several Se compounds were analyzed in water extract from selenized yeast by ion -
pair reversed-phase HPLC ICP MS and in nuts by SE ICP MS. Subsequent accurate
molecular mass determination by ESI-Q-TOF MS/MS identified several unknown
Se-glutathione species and selenopeptides. Despite th e emergence of liquid
chromatography as an efficient alternative to separate proteins, gel electrophoreses
is still the most widely used protein separation technique in life science disciplines.
Adapting the gel to a column and coupling it online to an ICP MS allowed DNA
fragments to be separated and quantified by monitoring the phosphor signal with
enhanced precision (<3%) compared to other conventional methods. Two ICP MS -
based methods for quantitative estimation of the phosphorylation level of a cellular

proteome were introduced, which accessed the native proteome state without
requiring the introduction of any label or derivatization. Enriched 111Cd isotope
was administrated to fish in chronic concentration so that the change in natural
isotope ratios (114Cd/111Cd) measured in metallothioneins by anion exchange ICP
MS clearly showed accumulation and distribution of Cd including redist ribution
from liver to kidney. Mercury, one of the largest threats to life, remains a problem
because of ongoing emission and deposition of inorganic Hg. In water and
sediments, bacteria convert mercury into methylmercury, which accumulates in the
food chain. Until now, the contribution of historical contamination and fresh
deposition could not be differentiated, blocking meas ures against the emitting
sources. Applying enriched 202Hg to natural environment and mercury speciation by
GC ICP MS revealed the distribution of mercury in environmental compartments
and its transformation to methylmercury, thereby quantifying for the fi rst time the
amount of methylmercury derived from fresh anthropogenic mercury emission
directly diverted to the food chain.
5) MOLECULE IDENTIFICATION CAPABILITIES OF HYPHENATED SYSTEMS:
In the course of element speciation, hyphenated ICP MS methods that can identify
compounds in well-defined cases are emerging frequently. In combination with the
aforementioned features, species identification makes hyphenated ICP MS a
fascinating and powerful analytical tool. In the case where only one single element
is detected from a molecule, identification capabilities depend entirely on its
retention time (tR) and the existence of a reference compound. The selectivity of the
coupled separation device has to guarantee that no other species present in the
injected sample and containing the same element appears at the same retention time.
However, this can conveniently be achieved by modern high -selectivity separation
techniques; at least by combining two or more of these (two - or multidimensional
separation70) eliminates any ambiguity. Additionally, most often the matrix itself
contains a drastically reduced number of possible species, or only a few are relevant
(e.g. toxic); so, typically, a small number of all known species have to be separated
from one sample. For stable and relevant species, CRMs are available, which allow
safe identification and accurate quantitation. This issue has recently become a
subject of debate in the arsenic speciation literature. Today, over As species of
diverse polarity (apolar, anionic, cationic) have been identified. There is,
however,no single procedure to individually separate these. Applying only one
separation procedure inevitably results in As species coelution.72 A safe
identification of coeluting organic As species can be done only by means of
selective detection as provided by electrospray tandem MS, requiring the
compounds for accurate quantitation. However, not many of these compounds are

present in a particular matrix, and an even lower number of these present a real
problem. So the selectivity of two-dimensional separation procedures hyphenated to
ICP MS is sufficient to identify these from most matrixes. This is valid as well in
bioinorganic speciation. SE chromatography is often used in combination with
another more selective liquid separation technique, e.g. ion exchange. Many metal –
protein interaction studies profit from the advantage of such LC techniques coupled
to ICP MS since this detector is much less restrictive to salt concentrations in the
mobile phases, providing a larger flexibility to adapt separation procedures.
Investigating metallo thioneins (MTs), Infante et al.have revealed the dominant role
of MT including single MT iso forms in sequestering Cd, Zn and Cu in fish living in
contaminated waters. Separating the proteins from liver and kidney by SE gave a
mixture of MT, which was compared to the total metal content in the tissue. The
mixture was further separated by ion-exchange chromatography to obtain the metal
distribution on single, separated MT iso forms. Species -unspecific calibration was
used by online isotope dilution and detection by ICP ToF MS.
6) SPECIES IDENTIFICATION INCLUDING ELEMENTAL RATIOS BY
HYPHENATED ICP MS:
Using the multielement capability and the ability to detect more than one element in
the same species provides elemental ratios as an additional criterion besides tR to
identify species. If no reference compound is used, the theoretical element ratio
expected from the stoichiometry is assumed to be identical to the stoichiometry of
the species under investigation. This might not be the case for complex and unstable
structures, which need additional confirmation of the structural features under the
actual experimental condition, e.g. by an exact molecular weight determination. A
good example was given by Hann et al., who detected Cu/S in proteins after SE
separation. Because of insufficient selectivity, the identification of a larger protein
relied exclusively on assumed Cu/S stoichiometry, which was verified by ESI MS
molecular weight determination. In this example, the Cu/S ratio was not found as
theoretically predicted since an unexpected S-bearing cysteine was lost during the
protein expression step. However, for smaller molecules, detecting several elements
during highefficiency separation drastically increases the reliability of species
identification by hyphenated ICP MS and can even be independent of retention
times. This has been demonstrated for chelators (e.g. EDTA, DTPA, CDTA, etc.),
each forming several strong metal complexes. According to t he variations in the
metal ionic radius, each metal forms a structurally different complex with the same
chelator, which was separated by high-performance gradient ion chromatography. It
has been shown that chelators found in the environment each gave a different metal
separation pattern that was distinct from all other chelators bound to the same metal.

Detection of a few metals allowed safe identification of each chelator according to
its unique separation pattern independently of retention times.
Sequentially detecting ICP MS instruments (all except ToF MS) are limited by the
number of multielement ratios they can detect during a chromatographic run. The
shorter the peak width, the lower the number of different m/z values that can be
sequentially determined. This means that the better the chromatographic separation
efficiency, the fewer the isotopes or elements that can be detected. Moreover,
isotope and element ratios of sequentially detected transient signals (peaks) are
skewed3 and need to be corrected.79 There is a need for the development of
simultaneous MS detection to prevent the progress made in separation efficiency to
increasingly restrict the applicability of MS in hyphenated systems. Currently,
sequential MS detection is a bottleneck that is una ble to measure in the same run all
the multielement species that a high-performance separation is able to resolve. This
brings detectors for mass spectrometry80 into the focus of instrument developers; a
mass spectrometer with a focal plane detector81 capa ble of simultaneously
accumulating signals has already been described.
SOLVED PROBLEMS 01
226) Which of the following is an example of anionic interference in atomic emission
spectroscopy?
(A) Interference of high concentration of sodium ions in assay calcium ions.
(B) Interference by formation of less volatile salt with sulphates by
calcium.
(C) Increased viscosity of the analyte solution by sugars.
(D) Decreased drop size of the analyte solution by alcohols.
227) Choose the correct sequence of process during Atomization in atomic absorption
spectroscopy
(A) Desolvation – Nebulization – Dissociation – Volatilization – Ionization ion
(B) Nebulization – Desolvation – Volatilization – Dissociation – Ionization ion
(C) Desolvation – Nebulization – Volatilization – Dissociation – Ionization
ion
(D) Nebulization – Volatilization – Desolvation – Dissociation – Ionization
228) Why is carbon used as an electrode in arc and spark sources?
1. Carbon is conductive 2. Has few emission lines 3. Easily shaped 4 . Thermally stable
5. Can be obtained in a very pure state 6. Available and relatively cheap 7. Inert
material
229) Axial view ICP instruments have some advantages and disadvantages as compared to
radial view instruments. Explain
Advantages of axial view ICP includes: 1. Wider linear dynamic range 2.
Lower detection limits 3. better suited for lower concentrations
Disadvantages of Axial view ICP includes: 1. suffers from self absorption
2. less convenient 3. radial view is preferred for higher concentrations

04-02-02: FLAME EMISSION SPECTROMETRY
1) INTRODUCTION & THEORY: In flame emission spectrometry, the sample solution is
nebulized (converted into a fine aerosol) and introduced into the flame where it is
desolvated, vaporized, and atomized, all in rapid succ ession. Subsequently, atoms and
molecules are raised to excited states via thermal collisions with the constituents of the
partially burned flame gases. Upon their return to a lower or ground electronic state, the
excited atoms and molecules emit radiation characteristic of the sample components. The
emitted radiation passes through a monochromator that isolates the specific wavelength for
the desired analysis. A photodetector measures the radiant power of the selected radiation,
which is then amplified and sent to a readout device, meter, recorder, or microcomputer
system.
Combustion flames provide a means of converting analytes in solution to atoms in the vapor
phase freed of their chemical surroundings. These free atoms are then transformed into
excited electronic states by one of two methods: absorption of additional thermal energy
from the flame or absorption of radiant energy from an external source of radiation.
In the first method, known as flame emission spectroscopy {FES), the energy from the
flame also supplies the energy necessary to move the electrons of the free atoms from the
ground state to excited states. The intensity of radiation emitted by these excited atoms
returning to the ground state provides the basis for analytical determinations i n FES.
 Flame emission spectroscopy is so named because of the  use of a flame to provide

the energy of excitation to atoms introduced into the flame.
 FES technique deals with the examination of the energy emitted from a substance
when suitably excited.
 It is a well known fact that alkali and alkaline earth metals can be detected by flame
test.

 All alkali and alkaline earth metal ions give characteristic colours in a Bunsen
flame.
 The brightness of the flame colour varies with the amount of sodium or other metal
introduced.
 Emission of such particular radiation by sodium or other metal and the correlation
of the emission intensity with the concentration of the element form the basis of
FES.
 It was formerly known as Flame photometry
2) PRINCIPLE:
 Desolvation: The metal particles in the flame are dehydrated by the flame and
hence the solvent is evaporated.
 Vapourisation: The metal particles in the sample are dehydrated. This also led
to the evaporation of the solvent.
 Atomization: Reduction of metal ions in the solvent to metal atoms by the
flame heat.
 Excitation: The electrostatic force of attraction between the electrons and
nucleus of the atom helps them to absorb a particular amount of energy. The
atoms then jump to the exited energy state.
 Emission process: Since the higher energy state is unstable the atoms jump
back to the stable low energy state with the emission of energy in the form of
radiation of characteristic wavelength, which is measured by the photo detector.
3) STEPS INVOLVED IN FES:

4) ADVANTAGES OF FES:
• It is generally more accurate, since automization  into a flame is more
reproducible method of introducing sample into the excited stale.
• It is rather a faster technique
• Detection sensitivity for alkali and alkaline metals is good
• As the number of lines is limited in the spectra it is easier to resolve and
identify individual member even in the presence of each other.
• Easy to carry out and requires not highly trained staff.
• The preparation of standard solutions is much easier than the other
spectroscopy methods.
5) DISADVANTAGES OF FES:
• Limited number of elements can be directly determined in the conventional
flames.
• The concentration of the elements which are not determined in the conventional
flames must be high.
• Solid substances cannot be used directly; hence preparation of their solutions is
a must.
• Instead of sharp lines, diffused bands of compounds such as CaO, Ca (OH) 2 and
Cu(OH) 2 often appear which can interfere in spectral separation.
SOLVED PROBLEMS 02
230) Ionization interference can be eliminated by addition of
(A) EDTA
(B) Cryolite
(C) Cesium salts
(D) Lanthanum chloride
231) In atomic emission spectroscopy the emission due to the electronic transition of
(A) Singlet ground state to singlet exited state
(B) Singlet exited state to singlet ground state.
(C) Singlet ground state to triplet exited state
(D) Triplet exited state to singlet ground state.
232) Why arc atomic emission methods with an ICP source better suited for multielement
analysis than arc flame atomic absorption methods?
AES with an ICP plasma source are better suited for multielement analysis than flame
AAS because no separate lamp is required for determination of each element in ICP.
All elements are atomized, excited in the ICP, and emission is analy zed. Emission
lines are separated by a good monochromator and resonance lines of all elements can
be directed to a multichannel detector.
233) What are the advantages and disadvantages of a flame photometer?
Flame photometers have the following advantages: 1. S imple atomic emission
instruments 2. Rugged and have a long working life 3. Relatively cheap 4. Fast
analysis time.However, flame photometers suffer from many disadvantages, including:
1. Low sensitivity 2. Applicable to few elements that can be easily atomized and
excited (Li, Na, K, Ca, and Mg) 3. Susceptible to flash -back

04-02-03: FLAME SPECTROMETRIC METHODS
INSTRUMENTATION FOR FLAME SPECTROMETRIC METHODS: The basic
components of flame spectrometric instruments are discussed in this section. These
components provide the following functions required in each method: (1) deliver the
analyte to the flame, (2) induce the spectral transitions (absorption or emission) necessary
for the determination of the analyte, (3) isolate the spectral lines required for t he analysis,
(4) detect the increase or decrease in intensity of radiation at the isolated lines(s), and (5)
record these intensity data.
Pretreatment of Sample : Flame FES requires that the analy1e be dissolved in a solution in
order to undergo nebulization (see the next section). The wet chemistry necessary to
dissolve the sample in a matrix suitable for either flame method is often an important
component of the analytical process. The analyst must be aware of substances that interfere
with the emission measurement. When these substances are in the sample, they must be
removed or masked (complexed). Reagents used to dissolve samples must not contain
substances that lead to interference problems.
Sample Delivery: The device that introduces the sample into the flame or plasma plays a
major role in determining the accuracy of the analysis. The most popular sampling method
is nebulization of a liquid sample to provide a steady flow of aerosol into a flame. An
introduction system for liquid samples consists of three components: (1) a nebulizer that
breaks up the liquid into small' droplets, (2) an aerosol. modifier that removes large
droplets from the stream, allowing only droplets smaller than a certain size to pass, and (3)
the flame or atomizer that converts the anaIyte into free atoms.
Nebulization: Pneumatic nebulization is the technique used in most atomic spectroscopy
determinations. The sample solution is introduced through an orifice into a high - velocity
gas jet, usually the oxidant. The sample stream may intersect the gas stream in either a
parallel or perpendicular manner (Figure 9.1a). Liquid is drawn through the sample
capillary by the pressure differential generated by the high -velocity gas stream passing over
the sample orifice. The liquid stream begins to oscillate, producing filaments. Finally, these
filaments collapse to form a cloud of droplets in the aerosol modifier or spray chamber. In
the spray chamber the larger droplets are removed from the sample stream by mixer paddles
or broken up into smaller droplets by impact beads (Figure 9.1 b) or wall surfaces. The
final aerosol, now a fine mist, is combined with the oxidizer/fuel mixture and carried into
the burner (Figure 9.2). A typical distribution range of droplet diameters is shown in Figure
9.3. Droplets larger than about 20 µm are trapped in the spray chamber and flow to waste.
The distribution of drop sizes is a function of the solvent as well as the components of the
sampling system. In AAS only a small percentage (usually 2% or 3%) of the nebulized
analyte solution reaches the burner.

Atomization: The atomization step must convert the analyte within the aerosol into free
analyte atoms in the ground state for FES analysis. Very small sample volumes (5 -100 ILL)
or solid samples can be handled by flameless electrothermal methods.
Flame Atomizers. The sequence of events involved in converting a metallic element, M,
from a dissolved salt, MX, in the sample solution to free M atoms in the flame is depicted
in Figure 9.4. After the aerosol droplets containing 1v.IX enter the flame, the solvent is
evaporated, leaving small particles of dry, solid 1v.IX. Next, solid 1v.IX is converted to
NIX vapor. Finally, a portion of the MX molecules are dissociated to give neutral free
atoms. The efficiency with which the flame produces neutral analyte atoms is of equal
importance in all the flame techniques. If the events proceed vertically from the top down
in Figure 9.4, the efficiency of free- atom production is high. Processes that branch
horizontally interfere with the production of free analyte atoms. These processes include:
(1) excitation and emission of radiation by MX(g) molecules, (2) reaction of M(g) atoms
with flame components at high temperatures to produce molecules and ions that also absorb
and emit radiation, and (3) formation of M+x ions, which, in addition to reducing the
efficiency of free-atom production,. complicate the analysis by adding lines to the
spectrum. The flame remains the most generally useful atomizer for atomic spectroscopy
despite the developments in electrothermal atomization. A satisfactory flame source must
provide the temperature and fuel/oxidant ratio required for a given analysis. The maximum
operating temperature of the flame is determined by the identities of the fuel and oxidant,
whereas the exact flame temperature is fixed by the fuel/oxidant ratio. In addition, the
spectrum of the flame itself should not interfere with the emission or absorption lines of the
analytes. Components of the flame gases limit the usable range to wavelengths longer than
210 nm.
Ionization Interference: At elevated flame and furnace temperatures, atoms with low
ionization potentials become ionized. Any ionization reduces the population of both the
ground state and the excited state of neutral fre e atoms, thus lowering the sensitivity of the
determination. This problem is readily overcome by adding an excess (ca. 100 - fold) of a
more easily ionized element such as K, Cs, or Sr to suppress ionization in both sample and
calibration solutions. The more easily ionized atoms produce a large concentration of
electrons in the vapor. These electrons, by mass action, suppress the ionization of analyte
atoms. Thus, suppressant should be added to samples that contain variable amounts of alkali
metals analyzed by acetylene/air flames to stabilize free-electron concentrations. The
addition of suppressants is even more important in analyses that require the hotter
acetylene/nitrous oxide flames.
INSTRUMENTATION OF SINGLE BEAM FLAME EMISSION SPECTROPHOTOMETER:
 High temperatures are necessary for elements which are not easily excited

 The various parts of flame photometer are sequentially shown
 Choices of Gases: It depends upon the type of element to be determined. Various

flames used are air-methane, air-illuminating gas, air-propane, etc.
 The flame temperature: It depends upon the type of gas mixture and on the mixing
ratio of the components. A hotter flame better vapourizes the sample. Higher
temperature promotes dissociation of non-emitting compounds.
 Gas Regulation: For quantitative flame photometry, a reproducible and steady
flame is required in advance. The flow of fuel gas and of oxygen or air to the flame
must be kept as uniform as possible.
 Flow rates of fuel and oxidant: For a given sample and instrument, both the
intensity and the steadiness received by the detector depends upon flow rates and
oxidant. In most instruments, these two are easily adjustable to certain limits.
 Introduction of sample into the flame: The uniform feeding of the sample or
standard into the region of excitation is very important for the accuracy of
procedure. For flame analysis the substance is generally dissolved in acid and then
sprayed with an atomizer. The aerosol of liquid droplets in air or oxygen is then
mixed with gas.

INSTRUMENTATION OF SINGLE BEAM FLAME EMISSION SPECTROPHOTOMETER:
The basic components for flame photometer are as follows:
 Burner
 Automizer
 Monochromators
 Detectors
 Read out device
Burners:
 The flame used in the flame photometer should possess following funct ions:
 The flame should have ability to evaporate the liquid droplets from the sample
solution in the formation of solid residue
 The flame should decompose the compounds in the solid residue resulting in the
formation of atoms.
 The flame must have the capacity to excite the atoms formed and cause them to emit
radiant energy.

 The mixture of mist, air or oxygen and fuel gas is conveyed to a burner,
above which the flame burns.
 There are also atomizers – burner combinations in which the liquid is
atomized and the oxygen and gas is mixed at the actual tip of the burner.
 Open Burners (Bunsen burner): Nowadays hardly used since flame easily
flashes back.
 Mecker Burner
 Total Cosumption Burner
 Premix or laminar-flow burner.
MECKER BURNER:
• For premixed flames the Mecker Burner is commonly used.
• Some Advantages of this burner is: The burner cap can be cooled easily. The
temperature of the flame is more uniform. The flame is steadier. The possibility
of flashing back of the flame is very rare.
 Some disadvantages are: 1) Producing relatively low flame,therefore, only alkali
metals can be studied. 2) Seldom used with highly explosive mixture of gases.
TOTAL CONSUMPTION BURNER:
• The name is given because the entire sample which enters the capillary tube will
enter the flame neglecting the size of droplet.

• Advantages: a) Atomization efficiency is 100% b) No flask back of the flame.
C) Combustible substances like gasoline can be safely sprayed.
• Disadvantages: a) Noisy and turbulent b) Losses due to incomplete evaporation
of the larger drops in the flame is observed. C) Mis -alignment of the atomizer
nozzle makes the flame lopsided (i.e. hanging lower on one side than the other)
PREMIX OR LAMINAR-FLOW BURNER:
 The most important advantage is that aspirated sample, fuel and oxidant are
premixed before they reach the opening of the burner.
 After thorough mixing they then enter the flame.
 The gas move in non-turbulent way.
 The important disadvantage of this burner is that a very small part (5%) of the
sample reaches the flame i.e. 95% of the sample is wasted.
 Hence this burner shows a poor or low sensitivity.
 This burner is noiseless, non-turbulent and stable. Decomposition of sample happens
easily and efficiency of atomization is great. The clogging of sample solution is
negligible.
MEASUREMENT OF EMISSION OF ATOMIC SPECIES:
 When atoms are excited light is emitted.
 The temperature must be high enough to evaporate the liquid components of the
sample entering the flame in form of mist, vaporize the residual solid particles int o
the gaseous state as completely as possible, and dissociate the molecules to form
free neutral atoms or radicals.
 Frequencies radiated by molecules and radicals are calculated by –
hv = E2 - E1 ……. (i)
Where, h = Plank’s constant

v = frequency of emitted light
E2 = internal energy of the excited molecule (higher energy level)
E1 = energy of the molecule after radiation of a photon (lower energy level)
Now v=c/λ
c = velocity of light
λ = wavelength
Therefore (i) equation hc/ λ = E2-E1 or λ = hc/ E2-E1
Knowing the value of λ, we can tell about the elements which are present in the
flame.
SOLVED PROBLEMS 03
234) In atomic absorption spectroscopy the most strongly absorbed light is called as
(A) Resonance line
(B) Base line
(C) Stokes line
(D) Anti stokes line
235) The sodium gives yellow color at 589.3 nm in flame. The wavelength of radiation for
the atomic absorption of sodium will be
(A) 767 nm
(B) 629,3 nm
(C) 549.3 nm
(D) 589.3 nm

236) What is Quantitative Analysis of ICP-MS.:
Quantitative analysis in ICP-MS is the fundamental tool used to determine
analyte concentrations in unknown samples. The instrument is cal ibrated
by measuring the intensity for all elements of interest in a  number of
known calibration standards that represent a range of concentrations likely
to be encountered in your unknown samples. Software creates a calibration
curve of the measured intensity versus concentration for each element in
the standard solutions.
237) What is ICP-MS?
Ans-Mass spectrometry (MS) is an analytical technique that ionizes
chemical species and sorts the ions based on their mass -to-charge ratio.
Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass
spectrometry which is capable of detecting metals and several non -metals
at concentrations as low as parts per billion on non -interfered low-
background isotopes.
04-02-04: INTERFERENCES IN EMISSION SPECTROSCOPY

1. The cross sensitivity
2. Background interferences
3. Spectral interferences
4. Anions interferences
5. Caton-cation interferences
6. The cross sensitivity:

The cross sensitivity interfering radiation consists of unwanted transmission by the
filter stray light in the monochromator, or in other words it is due to instrumental
inadequacy.
7. Background interferences: Background interferences cannot be entirely eliminated
by the instrument. It is always present at the wavelength of the analytical line or
band.
8. . Spectral interferences: It is caused due to two or more elements which have very
close emission lines that giveswrong results. It is caused due to high flame
temperature, due to which large number of spectral lines are produced.
9. Anions interferences: Anions can interfere as components of salts or acids and thus
serious analytical errors may occur. Anions like PO4 2 - , SO4 2- can cause
vapourization interference with alkaline earth metals through the formation of non -
volatile alkaline earth phosphates or sulphates in aerosol s particals.
10. Cation-cation interferences:
It can decrease the signal intensity of the metal present in the sample solution, like
interference of Na with K.
METHODS OF ANALYSIS:
• Calibration curve method / Standard addition method.
• Internal standard method.
• Simultaneous multi-element analysis.
• Calibration curve method - Standard addition method:The standard addition
technique involves adding known amounts of standard to one or more aliquots of the
processed sample solution, compensating for a sample constitue nt that enhances or
depresses the analyte signal.
• To prepare a calibration curve is the important part of this type of analysis.Firstly a
signal intensity of the unknown solution is recorded. In the second stage a series of
solutions containing unknown with the addition of different amounts of different
amounts of standard are prepared. The signal of each of these solutions is recorded.
Then a graph of concentration of unknown plus concentration of standard against the signal
intensity (Y-axis) is plotted. It is a straight line graph. From the graph, concentration of
unknown can be determined. This is possible when the straight line is extrapolated on the
concentration axis.
This method is useful when the concentration of the solution is very low. Most of th e
interferences can be overcome by this method. The analysis of rarely analyzed elements can
be done with the help of this method.
For accurate results the correction from background interference can be subtracted.

Internal standard method:
The various stages are
1. To a series of the standard solutions calculated amounts of internal standard element
(lithium) are added. Then the signal intensity is recorded for each of these solutions.
2. The signal intensity of unknown sample solution is recorded.
3. Then the graph of concentration against the ratio of signal intensities recorded as
above is plotted. The concentration of unknown element is calculated.
Simultaneous multi-element analysis:
To carry out such type of analysis different methods are available. In one of the methods a
monochromator is used. They reported spectral lines as close 20A0.
In the second method, a silicon diode vidicon detector system with a 0.5m monochromator
is used. Spectral lines 1.4A0 apart were resolved. Data on eight elements like Mo, F e, Ca,
Al, Ti, Mn, Co and K can be obtained simultaneously.
QUALITATIVE AND QUANTITATIVE APPLICATIONS OF FES:
Qualitative Analysis:
 It is comparatively a simple technique, fast and reliable.
 Structural information of compound present in the solution canno t be obtained from
this technique.
 Non-radiating elements like carbon, hydrogen and halides cannot be detected by this
technique.
Quantitative Analysis:
• Mainly the alkali and alkaline earth elements are determined quantitatively.
• The concentration of the element in given sample can be determined by
Standard Addition Method
Internal Standard Method

Simultaneous Multi-element Analysis.
APPLICATIONS: Most applications of FES have been the determination of trace metals,
especially in liquid samples. It should be remembered that FES offers a simple,
inexpensive, and sensitive method for detecting common metals, including the alkali and
alkaline earths, as well as several transition metals such as Fe, Mn, Cu, and Zn. FES has
been extended to include a number of nonmetals: H, B, C, N, P, As, O, S, Se, Te, halogens,
and noble gases. FES detectors for P and S are commercially available for use in gas
chromatography. FES has found wide application in agricultural and environmental
analysis, industrial analyses of ferrous metals and alloys as well as glasses and ceramic
materials, and clinical analyses of body fluids. FES can be easily automated to handle a
large number of samples. Array detectors interfaced to a microcomputer system permit
simultaneous analyses of several elements in a single sample.

General Applications:
• Agriculture and Botany
• Foods and Nutrition
• Medicine and Biology
• Geology, Industry and fields
• Chemical and Pharmacy
• Paper industry and industrial waste processing
• Analysis of geological materials such as minerals, ores, clay etc
• Glass and ceramic industries.
SOLVED PROBLEMS 04
238) Atomic absorption spectra produce narrow brand with peaks generally called as lines
because it involves
A) Electronic transition only
(B) Vibrational transitions only

(C) Rotational transitions only
(D) All of the three transitions
239) The range of temperatures attainable by acetylene -air mixture is
(A) 2550-2700
(B) 2000-2100
(C) 3050-3150
(D) 2100-2400
240) What exposure time and numbers of average for multichannel spectrometers
i am using a 4-channel spectrometer for atmospheric pressure plasma

spectroscopy. For every channel, I used to set a own exposure time (with
the auto exposure setting of my software) so that the max intensity of
each channel is at 80% of the max intensity. The times range from
several milliseconds to 1 second. Additionally, I average 10 spectra for
every channel.
241) Why is a molecular oxygen band not observed in an emission spectrum of air
discharge?
In the literature for emission spectrum for air discharge only molecular
nitrogen, atomic oxygen, and Nox formation is described. But absence of
molecular oxygen in air discharge is not explained. Is it that the energy
required for molecular oxygen to get in excited state is very large?
CHECK POINT 04-02

1) In atomic emission spectroscopy the graph drawn between
2) Solid samples can be directly analyzed by use of
3) The main advantage of atomic emission spectroscopy over the atomic absorption
spectroscopy is
4) Releasing agents are used in atomic emission spectroscopy to prevent
SUMMARY
This method is useful when the concentration of the solution is very low. Most of the
interferences can be overcome by this method. The analysis of rarely analyzed elements can
be done with the help of this method
KEY WORDS
Inductively coupled plasma mass spectrometry; sample introduction; total element
quantitation; element speciation; species identificat ion

REFERENCES
Benue, Makurdi, Nigeria. International Journal of Environment and Bioen ergy 8:56-67.
contents in samples of different medicinal plants. International Journal of Chemical Science
9(3):1126-1132.
1) Emission Vs wave length
2) Graphite furnace absorption spectroscopy
3) Analysis of multiple elements simultaneously
4) Anionic interference
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=2tJqZStFwjU
https://www.youtube.com/watch?v=HEOO5zSPNRI
WIKIPEDIA
https://en.wikipedia.org/wiki/Atomic_emission_spectroscopy
https://www.sciencedirect.com/topics/chemistry/plasma -atomic-emission-spectroscopy
OER
____
REFERENCE BOOKS
1. Deewan SK. Organic spectroscopy (N.M.R., I.R., Mass and UV).New Delhi:CB S
2. William K. Organic Spectroscopy. Macmillan: Macmillan Chemistry Text; 1991.
3. Beckett AH, Stenlake JB. Practical Pharmaceutical Chemistry: Part -II. London:The
4. Verma RM, Analytical Chemistry: Theory and Practice. Third Edition. New Delhi:
CBS Publishers and Distributors Pvt. Ltd.; 2006.
5. Ravi Sankar S., Text Book of Pharmaceutical Analysis, Tiruneliveli:Rx Publications:
2006.

CREDIT 04-UNIT 03: INTRUMENTATION & INTERFERENCE
APPLICATIONS OF AAS
LEARNING OBJECTIVES
 Define atomic absorption spectroscopy (AAS)
 Describe the principle involved in AAS
 Enumerate the interferences that affect AAS
 Explain the instrumental components and t heir working
 Apply the knowledge in pharmaceutical quality control of drugs
INTRODUCTION
This section should present an open ended question or discuss some interesting information
along with relevant image so as to arouse curiosity of learners about this unit topic.
04-03-01: PRINCIPLE
Atomic-absorption spectroscopy (AAS) uses the absorption of light to measure the
concentration of gas-phase atoms. Since samples are usually liquids or solids, the analyte
atoms or ions must be vaporized in a flame or graph ite furnace. The atoms absorb
ultraviolet or visible light and make transitions to higher electronic energy levels. The
analyte concentration is determined from the amount of absorption. Applying the Beer -
Lambert law directly in AAS is difficult due to var iations in the atomization efficiency from
the sample matrix, and non-uniformity of concentration and path length of analyte atoms (in
graphite furnace AAS). Concentration measurements are usually determined from a working
curve after calibrating the instrument with standards of known concentration.
“Atomic Absorption Spectroscopy is an absorption method where radiation is absorbed by

nonexcited atoms in the vapour phase i.e. nebulized state.”

The principle of AAS is based on the absorption of energy by gro und state atoms in the
gaseous state.
When a solution having metal is introduced to flame the vapour of metal is obtained. Then
some metal atoms may get raised to higher levels of energy to emit the radiations. But
majority of atoms remain unexcited. When a light of specific resonance wavelength is
passed through a flame having atoms of the metallic species, part of light will be absorbed
& absorption will be proportional to the density of atoms in flame.
Therefore, the total amount of light absorbed is
Where, e= charge on electrons

m=mass of light
N=total no. of atoms that can absorb at frequency ‘v’ in light path
f= oscillar strength
c=speed of light.
From the above expression we can conclude that, absorption of light by an atom is
independent of wavelength of absorption and the temperature of the atoms. But temperature
affects the efficiency at which atoms are produced from a sample. The temperature of
ignition is 2100° – 2800° C. The characteristic / specific resonance wavelength is obtained
from a lamp whose cathode is made up of the same element that is to be determined. A
Photomultiplier tube is used to detect the reduction in intensity of light. The AAS is also
called as Atomic Flame Photometry as sample solution is sprayed into the flame the whole
technique is carried out in the UV-regions.
DIFFERENCE BETWEEN AAS AND FES:

ATOMIC ABSORPTION SPECTROSCOPY:
 Measures the radiation absorbed by the unexcited atoms
 Variation in temperature does not cause any change on the larger number of
unexcited atoms i.e. negligible.
 Hence absorption intensity is not affected by the intensity of the flame
 Relation between absorbance and concentration is linear i.e. Beer’s law is obeyed.
FLAME EMISSION SPECTROSCOPY:
• Measures the radiation emitted by the excited atoms
• Variation in temperature causes greater changes in the number of excited atoms.
• Hence emission intensity is affected to a larger extent by the intensity of the flame
(i.e. Temperature).
• Relation between emission and concentration is non -linear.

SOLVED PROBLEMS 01
242) Which of the following is not descriptive of a photomultiplier tube:
a) emits electrons proportionally to initial light absorbed
b) must be shielded from stray light
c) cannot be used with a chopper
d) amplifies the initial signal received
243) Which of the following is false about a photomultiplier tube:
a) converts radiant energy (light) to electrical energy (current)
b) amplifies the current significantly
c) has a very rapid response time
d) is composed of an iron plate and a layer of selenium
244) Why a continuous source like D2 lamp or tungsten lamp can not be used in atomic
absorption spectroscopy?
A monochromator is needed to block out radiation of wavelengths not
absorbed by the analyte, otherwise a significant amount of radiat ion, whose
intensity is unaffected by analyte concentration, reaches the detector, and
prevents a linear response between absorbance and concentration. This was
a problem for atomic absorption measurements, where the bandwidth of the
atomic absorption line is typically 0.005 nm. Relatively inexpensive
monochromator system currently available do no resolve better than 0.1 nm
and therefore, the normal radiation sources (deuterium and tungsten) cannot
be used.
245) How does the HCL lamp work?
Applying a high voltage across the electrodes causes ionisation of the inert
gas. The gaseous ions move rapidly towards the cathode and dislodge some
of the metal atoms from the cathode and produce an atomic cloud, a process
is known as sputtering. Some of the sputtered metal atoms are in the excited
state, and will emit the characteristic set of frequencies when returning to
the ground state. Eventually, the metal atoms diffuse back to the cathode or
to the glass walls of the tube and are redeposited.
04-03-02: HIGH SENSITIVITY SAMPLING SYSTEMS

LIMITATIONS TO FLAME AA SENSITIVITY:
Flame atomic absorption is a rapid and precise method of analysis. Determinations of
analyte concentrations in the mg/L concentration region are routine for most elements.
However, the need for trace metal analyses at mg/L and even sub mg/L levels calls for a
more sensitive technique.
For atomic absorption to occur, free ground state atoms must be placed in a beam of light of
a wavelength corresponding to an appropriate electron transition of the anal yte. Any

sampling process conceived must therefore address the process of creating ground state
atoms and directing them to the spectrometer light path.
In examining the flame AA process, we can find a number of areas limiting the sensitivity
of the technique. The absorbance depends on the number of atoms in the optical path of the
spectrometer at a given instant. The nebulization process, which draws sample solution into
the burner chamber at approximately 3 -8 milliliters per minute, limits the sample
introduction rate, and, therefore, the amount of sample available for transport to the flame.
Further, the premix burner design, which has been universally adopted due to its many
desirable characteristics, has the undesirable characteristic of being very wast eful of
sample. Only a small fraction of the sample nebulized ever reaches the flame, with the
remainder being directed to the drain. Finally, that sample which is introduced into the
flame is resident in the light path for only a fleeting moment as it is propelled upwards
through the flame.
The sensitivity of atomic absorption can be improved by addressing the limitations of flame
sampling. By improving the sampling efficiency and/or constraining analyte atoms to the
light path for a longer period of time, a greater absorption for the same analyte
concentration can be achieved.
THE COLD VAPOR MERCURY TECHNIQUE:
Principle
Since atoms for most AA elements cannot exist in the free, ground state at room
temperature, heat must be applied to the sample to break t he bonds combining atoms into
molecules. The only notable exception to this is mercury. Free mercury atoms can exist at
room temperature and, therefore, mercury can be measured by atomic absorption without a
heated sample cell.
In the cold vapor mercury technique, mercury is chemically reduced to the free atomic state
by reacting the sample with a strong reducing agent like stannous chloride or sodium
borohydride in a closed reaction system. The volatile free mercury is then driven from the
reaction flask by bubbling air or argon through the solution. Mercury atoms are carried in
the gas stream through tubing connected to an absorption cell, which is placed in the light
path of the AA spectrometer. Sometimes the cell is heated slightly to avoid water
condensation but otherwise the cell is completely unheated.
As the mercury atoms pass into the sampling cell, measured absorbance rises indicating the
increasing concentration of mercury atoms in the light path. Some systems allow the
mercury vapor to pass from the absorption tube to waste, in which case the absorbance
peaks and then falls as the mercury is depleted. The highest absorbance observed during the
measurement will be taken as the analytical signal. In other systems, the mercury vapor is
rerouted back through the solution and the sample cell in a closed loop. The absorbance

will rise until an equilibrium concentration of mercury is attained in the system. The
absorbance will then level off, and the equilibrium absorbance is used for quantitation.
The entire cold vapor mercury process can be automated using flow injection techniques.
Samples can be analyzed in duplicate at the rate of about 1 sample per minute with no
operator intervention. Detection limits are comparable to those obtained using manual bat ch
processes. The use of flow injection systems also minimizes the quantity of reagents
required for the determination, further reducing analysis costs.
Advantages of the Cold Vapor Technique:
The sensitivity of the cold vapor technique is far greater than can be achieved by
conventional flame AA. This improved sensitivity is achieved, first of all, through a 100%
sampling efficiency. All of the mercury in the sample solution placed in the reaction flask is
chemically atomized and transported to the sample cell for measurement.
The sensitivity can be further increased by using very large sample volumes. Since all of
the mercury contained in the sample is released for measurement, increasing the sample
volume means that more mercury atoms are available to be transported to the sample cell
and measured. The detection limit for mercury by this cold vapor technique is
approximately 0.02 mg/L. Although flow injection techniques use much smaller sample
sizes, they provide similar performance capabilities, as the en tire mercury signal generated
is condensed into a much smaller time period relative to manual batch -type procedures.
Where the need exists to measure even lower mercury concentrations, some systems offer
an amalgamation option. Mercury vapor liberated from one or more sample aliquots in the
reduction step is trapped on a gold or gold alloy gauze. The gauze is then heated to drive
off the trapped mercury, and the vapor is directed into the sample cell. The only theoretical
limit to this technique would be that imposed by background or contamination levels of
mercury in the reagents or system hardware.
Limitations to the Cold Vapor Technique:
Of all of the options available, the cold vapor system is still the most sensitive and reliable
technique for determining very low concentrations of mercury by atomic absorption. The
concept is limited to mercury, however, since no other element offers the possibility of
chemical reduction to a volatile free atomic state at room temperature.
HYDRIDE GENERATION TECHNIQUE:
Principle
Hydride generation sampling systems for atomic absorption bear some resemblances to cold
vapor mercury systems. Samples are reacted in an external system with a reducing agent,
usually sodium borohydride. Gaseous reaction products are then carried to a sampling cell
in the light path of the AA spectrometer. Unlike the mercury technique, the gaseous reaction
products are not free analyte atoms but the volatile hydrides. These molecular species are

not capable of causing atomic absorption. To dissoci ate the hydride gas into free atoms, the
sample cell must be heated.
In some hydride systems, the absorption cell is mounted over the burner head of the AA
spectrometer, and the cell is heated by an air-acetylene flame. In other systems, the cell is
heated electrically. In either case, the hydride gas is dissociated in the heated cell into free
atoms, and the atomic absorption rises and falls as the atoms are created and then escape
from the absorption cell. The maximum absorption reading, or peak height, o r the
integrated peak area is taken as the analytical signal.
Advantages of the Hydride Technique:
The elements determinable by hydride generation are listed in Table 4 -1. For these
elements, detection limits well below the mg/L range are achievable. Like cold vapor
mercury, the extremely low detection limits result from a much higher sampling efficiency.
In addition, separation of the analyte element from the sample matrix by hydride generation
is commonly used to eliminate matrix-related interferences.
The equipment for hydride generation can vary from simple to sophisticated. Less
expensive systems use manual operation and a flame -heated cell. The most advanced
systems combine automation of the sample chemistries and hydride separation using flow
injection techniques with decomposition of the hydride in an electrically -heated,
temperature-controlled quartz cell.
Disadvantages to the Hydride Technique:
The major limitation to the hydride generation technique is that it is restricted primarily to
the elements listed in Table 4-1. Results depend heavily on a variety of parameters,
including the valence state of the analyte, reaction time, gas pressures, acid concentration,
and cell temperature. Therefore, the success of the hydride generation technique will vary
with the care taken by the operator in attending to the required detail. The formation of the
analyte hydrides is also suppressed by a number of common matrix components, leaving the
technique subject to chemical interference.
GRAPHITE FURNACE ATOMIC ABSORPTION:
Principle
By far the most advanced and widely used high sensitivity sampling technique for atomic
absorption is the graphite furnace. In this technique, a tube of graphite is located in the
sample compartment of the AA spectrometer, with the li ght path passing through it. A small
volume of sample solution is quantitatively placed into the tube, normally through a sample

injection hole located in the center of the tube wall. The tube is heated through a
programmed temperature sequence until finally the analyte present in the sample is
dissociated into atoms and atomic absorption occurs.
As atoms are created and diffuse out of the tube, the absorbance rises and falls in a peak -
shaped signal. The peak height or integrated peak area is used as the an alytical signal for
quantitation.
Advantages of the Graphite Furnace Technique:
Detection limits for the graphite furnace fall in the ng/L range for most elements. The
sample is atomized in a very short period of time, concentrating the available atoms in the
heated cell and resulting in the observed increased sensitivity. Even though this technique
uses only microliter sample volumes, the small sample size is compensated by long atom
residence times in the light path. This provides detection limits similar to the techniques
discussed above which use much larger samples.
The graphite furnace is much more automated than the other techniques. Even though
heating programs can be very sophisticated, the entire process is automated once the sample
has been introduced and the furnace program initiated. Automatic samplers make
completely unattended operation for graphite furnace AA possible.
Early experiences with the graphite furnace were plagued with interference problems,
requiring detailed optimization procedures for every sample to obtain accurate results.
However, extensive studies into the theory of the furnace technique combined with the
development of improved instrumentation have changed furnace AA into a highly reliable,
routine technique for trace metal analysis.
The final and most obvious advantage of the graphite furnace is its wide applicability. The
graphite furnace can determine most elements measurable by AA in a wide variety of
matrices. The importance of this technique requires a more detailed disc ussion in the
following chapters.
SOLVED PROBLEMS 02
246) When performing spectrophotometer quality assurance checks, what is the holmium
oxide glass filter used to assess
a) linearity
b) stray light
c) absorbance accuracy
d)wavelength accuracy

247) Which of the following is not a problem inherent in turbidemetry:
a)variation in particle size of samples
b)variation in particle size of standards
c)rate of aggregation or settling of particles
d)need to maintain a constant and specific temperature
248) What is the purpose of an internal standard in flame emission methods?
The purpose of an internal standard in flame emission spectroscopy is to
correct for small fluctuations in flame temperature as well as correction for
fluctuations in sample aspiration rate.
249) Suggest sources of the two signals in the figure above that appear during the drying
and ashing processes.
The appearance of peaks during drying and ashing processes could be
attributed to formation of particulates which result in scattering. Al so,
volatile molecular species formed during these processed obviously
contribute to observed signals.
04-03-03: INTRUMENTATION
Instrumentation of Atomic Absorption Spectroscopy:
Instrumentation:
A typical AAS has the following instrumental components in i t
i. Radiation Source
2) Flame Neublization Unit (Atomizer)
3) Monochromator& Filter
4) Detector
5) Amplifier& Read out Devices
1) Radiation Source:
The radiation source is responsible for emitting continuous spectra of the elements to be
determined and these spectra should have sharp lines. To obtain best results a
spectrophotometer with high dispersion is required along with expanded scale recorder, So
as to cover a larger area of spectral region.

Examples: Hollow Cathode Discharge lamp, Electrodeless Disc harge lamps.
A] Hollow Cathode Discharge Lamp
When a current in the milliampere range arises, the inert gas is charged at the anode
 The lamp window is made up of quartz or silica or glass.
 The Anode is a tungsten wire. The two electrodes are present in atube containing inert
gas.
 The cathode consists of a hollow cup made up of the element which is to be determined.
eg:- Na
The Anode is a tungsten wire. The two electrodes are present in atube containing inert gas.
 The lamp window is made up of quartz or silica or glass.
 When a current in the milliampere range arises, the inert gas is charged at the anode
& charged gas is charged at anode & charged gas is attracted at high velocity to the
cathode. The impact with cathode vaporizes some of the Sodium at oms. They get
excited and when return to the ground state give rise to Na emission.
 The inert gas is used for –
1) It’s main source of current – carrying capacity in hollow cathode.
2) It dislodges atoms from the surface of cathode.
3) It’s primarily responsible for excitation of the ground state metal atoms.
Removal of atoms by positive ions of inert gas that is bombarded on the cathode is called as
Sputtering. The pressure is maintained at 1-5 torr, as higher pressure leads to unstable
discharge and in lower Pressure vaporization of cathode metal increases & the operating
temperature also increases.
1. IONIZATION
2. SPUTTERING
3. EXCITATION
4. EMISSION
In Atomic Absorption Spectrometry, the line spectrum of the element being analyzed is
emitted from a HCL and passes through the optics of the instrument. The atomized sample
is introduced into the flame and absorbs resonance lines from the line spectra of the
element. The decrease in the light intensity of the resonance lines is related to the
concentration of the analyte by the Beer-Lambert Law in a similar fashion to other
absorption methods, that is,
A = -log T = kc

As the name suggests the lamp consists of 2 parts (anode and cathode) and is filled with an
inert gas (generally Ar or Ne). The HCL is connected to a r egulated low voltage low current
DC power supply. The flowing electrical current causes excitation of the element present on
the cathode and generates the characteristic line spectra of that element. The shape and
configuration of the HCL helps to focus the radiation into the optical path of the
instrument. Generally, one uses the specific HCL for the element being analyzed. Each
specific HCL has specified current settings, so be sure to adjust the DC power supply to be
within the operational parameters of that lamp. The reason for using the line source of the
element for the radiation source is its very narrow and well -defined lines. The bandwidth of
a selected line may approach 0.005 nm, something that most monochromators could not
accomplish.
Signal Modulation by Chopper:
In AAS to avoid interferences caused by emission of radiation by flame, the output of the
source must be modulated to provide a fluctuating intensity at a constant rate. The detector
receives two types of signal, an alternating one from t he source and a continuous one from
the flame. Later they are converted into the corresponding types of electrical responses. To
achieve these kind of signal modification a circular metal disc or chopper is interposed in
between the source and the flame. Alternate quadrants of the disk are removed to permit
passage of light. Rotation of the disk at constant known rate produces a beam that is
chopped to the desired frequency.
2) Flame Neublizer (Atomizer):
In AAS to achieve absorption of atoms of the sample sample is reduced to it’s
corresponding atomic state. This process of converting the sample into a atomic state is
called Atomization or Neublization
It can be achieved by the following equipments –
a) Ovens: The sample is brought rapidlyat high temperature.
b) Electric Arcs and Sparks: Here a high current or high voltage alternatively current spark
is applied to solid / liquid samples.
c) Sputtering Devices: In this, the sample held on a cathode is bombarded b y positive ions
of an inert gas.
d) Flame Atomizers: Here the liquid sample is converted into gaseous state by use of a
flame.
The fuel & oxidant gas are fed into a mixing chamber, where they proceed through series of
baffles to the burner head. The flame orifice is in form of a long narrow slot, so that ribbon
flame is produced .The sample in solution is aspired into the mixing chamber by a small air
jet into a premixed gas air burner designed for a long path length. The radiation is passed
into the monochromator and measured at the detector. The amount of radiation absorbed is

passed into the concentration of the element in the sample .A calibration curve is prepared
by measuring the absorbance of series of standard solutions.
Flame inAAS:
Some of the commonly used fuels and their relative data:
Types of burners used in Atomic Absorption:
There are 2 types of burners used in Flame Absorption method: -
1)Total Consumption Burner: In Total Consumption Burner the liquid sample ,the fuel &
oxidizing agents are passed through separate passages to meet at the opening of the base of
the flame . It uses hydrogen with oxygen or acetylene to give very hot flames.
Advantages:
 Representative sample reaches the flame.
 As amount of sample in flame is large, the sensitivity increases.
 There is no explosion hazards.
Disadvantages:
 Short path leads to lower sensitivity.
 Poor reproducibility results because of non uniform droplet size.
 Large droplets may clog as they are not completely decomposed.
2) Premixed Burner: In premixed burner, a mixture of the sample & premixed g ases is
allowed to enter the instrument. Which later passes to the flame re gion and atomization
takes place.
Advantages:
 Long path provides sensitivity.

 It has a very little tendency to clog.
 Only small drops reach flame so better reproducibility is obtai ned.
Disadvantages:
 Rate of introduction of sample is low.
 Chances of explosion in mixing chamber.
 Analytical errors are caused due to selective evaporation of mixed solvents.
Flame aspiration :
Ethyne/air (giving a flame with a temperature of 2200 –2400°C) or ethyne/dinitrogen oxide
(2600–2800°C) are often used. A flexible capillary tube connects the solution to the
nebuliser. At the tip of the capillary, the solution is ‘nebulised’ – ie broken into small drops.
The larger drops fall out and drain off while smaller ones vaporise in the flame.
Advantages of Flame Atomizers:
1.They are convenient ,reliable and relatively free of memory effects.
2.Most of the flames used are noiseless and safe to operate.
3.Burner systems are small ,inexpensive and durable.
4.Sample solutions are easily handled with simple neublisers.
5.A variety of flames can be used to select optimum working conditions for a wide variety
of elements.
Disadvantages of Flame Atomizers :
1.The sample volume available may be less than 3 -10ml.Theanalyte concentration may be
too low to allow dilution of the sample .
2.Pneumatic neublisers are only capable of introducing 10% of the sample into the flame.
3.Flames are rarely able to atomise solid samples or viscous liquid samples directly .
4.Flame background absorption and emission often requires some sort of correction
procedure.
Electrothermal atomization:
It provides enhanced sensitivity as the entire sample is atomized in a short period and the
average residence time of the atoms in the optica l path is a second or more. A hollow
graphite tube with a platform.25 µl of sample is placed through the sample hole and onto
the platform from an automated micropipette and sample changer. The tube is heated
electrically by passing a current through it in a pre-programmed series of steps. The details
will vary with the sample but typically they might be 30 –40 seconds at 150°C to evaporate
the solvent, 30 seconds at 600°C to drive off any volatile organic material and char the
sample to ash, and with a very fast heating rate (1500 °C s) to 2000–2500°C for 5–10
seconds to vaporise and atomised elements (including the element being analysed).Finally
heating the tube to a still higher temperature(2700°C) cleans it ready for the next sample.
During this heating cycle the graphite tube is flushed with argon gas to prevent the tube

burning away. In electrothermal atomisation almost 100% of the sample is atomised. This
makes the technique much more sensitive than flame AAS.
Advantages of Electrothermal Atomisers :
1.Unusually high sensitivity for small samples(0.5 -10mg/ml)
2.Decreased sample size.
3.In situ sample treatment.
4.Direct analysis of solid samples.
5.Unattended operation ,safety of operation.
Disadvantages of Electrothermal Atomisers :
1.Relatively poor precision compared to flame techniques(<1%)
2.Furnace techniques are slow(5-10 min.s)per sample.
3.Small samples are not easily detected.
4.More chances of interferences.
3) Monochromator & Filter:
The monochromator is used to select a given line in the emission spectrum of the light
source and isolate it from all other lines. eg : - Prisms & Gratings. For AAS the instrument
should produce a sufficiently narrow band width to separate the line chosen for
determination from other undesirable lines that may either interface with the measurement
or decrease the sensitivity of the analysis. For alkali metals having a few widely spaced
resonance lines in visible region a glass filter is used .
4) Detectors:
For AAS; Photomultiplier Tube (PMT) is used .It has a good stability when used with a
stable power supply. In PMT, there is an evacuated envelope which contains a photo
cathode, a series of electrodes called dynodes and an anode. The photocathode is fixed to
the terminal of power supply .When photon strikes the photocathode , an electron is
dislodged and the photon is accelerated to dynode 1 ,which gives 2 or more electrons from
dynode 1 .Electron from dynode 1 are accelerated to dynode 2, which further gives more
electrons . Thus the current multiplied at each dynode and the resultant electron current is
received by the anode to produce an EMF across the circuit which goes to the external
amplifier & read out system.
5) Amplifier & Reader :

The PMT output is taken to an amplifier which itself operates at the source modification
frequency .It includes digital displays & often graphical presentation of data is seen on
video display unit or external computers. A hard copy can also be made on chart recorders.
But care3 should be taken to prevent the use of highly luminous flames should always
avoided;otherwisw the detector may be saturated due to continuous signal increase .
Applications:
The following are the some of the important applications seen recent days in then field of
Atomic Absorption Spectroscopy:-
1) Qualitative Analysis: Due to requirement of separate hollow cathode lamp for each
sample it is rarely used for Qualitative analysis.
2) Quantitative Analysis: The AAS is very sensitive and is accurate than any other
technique. The different factors effecting quantitative determination are –
a)Flame System ,b)Wavelength Selection ,c) Solution.
3) Simultaneous Multicomponent Analysis : If a multi -element emission source is available
,then multi-component analysis can be carried out
4) Determination of metallic Elements in Biological Materials
5) Determination of Metallic Elements in Food Industry:The toxic levels of Co,Ni&Zn
levels in food items are detected by AAS.
6) Determination of Clacium ,Magnesium,Sodium& Potassium in Blood Serum
7)Determination of Lead in Petrol : Tetra ethyl & Tetra methyl lead are present in petrol or
the combination is present which is checked by AAS.
8)Determination of low levels of arsenic using FlameAAS &ultraAA Lamps. 9)Extending
analysis range of Gold using ultrAA Lamps.
10)Analysis of Iron ores.
11)Analysis of Cement.
12) Determination of Calcium in Saliva
13)Application of atomic-absorption spectroscopy in physics research
14)Determination of Cobalt in Steel, Alloy Steel and Nickel
SOLVED PROBLEMS 03
250) Which of the following instruments is used in the clinical laboratory or in reference
laboratories to detect beta and gamma emissions
a)fluorometer
b)nephelometer
c)scintillation counter
d)spectrophotometer
251) What is the function of the flame in atomic absorp tion spectroscopy

a)absorb the energy emitted from the metal analyte in returning to
ground state
b)supply the thermal energy needed to excite the metal analyte
c)bring the metal analyte to its ground state
d)supply the light that is absorbed by the metal analyte
252) What is the problem with reducing the slit width of the monochromator to get a
narrower line?
The problem with reducing the slit width is that it reduces the number of
photons or source power reaching the sample. Reducing the slit width on
a continuum source to a level that would provide a narrow enough line to
respond to atomic absorption would reduce the power so that it would
not be much above the noise. Therefore, hollow cathode lamps, which
emit intense narrow lines of radiation specific to the element being
analyzed, are needed for atomic absorption measurements.
253) Can you devise a strategy to overcome unwanted ionization of the analyte?
One possibility might be to use a cooler atomization source, although
there are limitations on the range to which this is feasible. The RF power
used in an inductively coupled plasma does influence the temperature of
the plasma, and there are recommendations for specific elements about
the recommended source power. Similarly, changes in the fuel/oxidant
ratio cause changes in the temperature of a flame.
254) What is the principle of flame spectroscopy?

255) Which fuel is used in flame photometry?
256) What is flame emission spectroscopy used for?
257) What is flame emission spectroscopy used in steel indust ry?
04-03-04: INTERFERENCES
AAS is less liable to be affected by interferences then compared to flame photometric
techniques this technique is especially free from cationic interferences because the
absorption of resonance lines from hollow cathode lamp. H owever it has the following
interferences which needs deep knowledge and practice.
Since the concentration of the analyte element is considered to be proportional to the
ground state atom population in the flame, any factor that affects the ground state
population of the analyte element can be classified as interference. Factors that may affect
the ability of the instrument to read this parameter can also be classified as interference.
The following are the most common interferences:
b. Spectral interferences are due to radiation overlapping that of the light source. The
interference radiation may be an emission line of another element or compound, or
general background radiation from the flame, solvent, or analytical sample. This usually
occurs when using organic solvents, but can also happen when determining sodium with
magnesium present, iron with copper or iron with nickel.
c. Formation of compounds that do not dissociate in the flame. The most common example
is the formation of calcium and strontium phosphates .

d. Ionization of the analyte reduces the signal. This is commonly happens to barium,
calcium, strontium, sodium and potassium.
e. Matrix interferences due to differences between surface tension and viscosity of test
solutions and standards.
f. Broadening of a spectral line, which can occur due to a number of factors. The most
common line width broadening effects are:
1. Doppler effect:
This effect arises because atoms will have different components of velocity along the line
of observation.
2. Lorentz effect:
This effect occurs as a result of the concentration of foreign atoms present in the
environment of the emitting or absorbing atoms. The magnitude of the broadening varies
with the pressure of the foreign gases and their physical properties.
3. Quenching effect:
In a low-pressure spectral source, quenching collision can occur in flames as the result of
the presence of foreign gas molecules with vibration levels very close to the excited state of
the resonance line.
4. Self-absorption effect:
The atoms of the same kind as that emitting radiation will absorb maximum radiation at the
center of the line than at the wings, resulting in the change of shape of the line as well as
its intensity. This effect becomes serious if the vapor, which is absorbing radiation is
considerably cooler than that which is emitting radiation.
SOLVED PROBLEMS 04
258) Which of the following is the principle of Atomic Absorption Spectroscopy?
a)Radiation is absorbed by non-excited atoms in vapour state and are excited to
higher states
b) Medium absorbs radiation and transmitted radiation is measured
c) Colour is measured
d) Colour is simply observed
259) In Atomic Absorption Spectroscopy, which of the following is the generally
used radiation source
a) Tungsten lamp
b) Xenon mercury arc lamp
c) Hydrogen or deuterium discharge lamp
d) Hollow cathode lamp

260) Why is an electrothermal atomizer more sensitive than a flame atomizer?
Electrothermal atomizers rapidly atomize the sample i n a short burst,
producing a locally higher concentration of free analyte atoms per unit
of time in the optical path than is possible with a rapidly flowing flame
atomization source. This higher “effective concentration” allows for
greater sensitivity than with a flame. Essentially, more of the analyte

atoms have a chance to stay in the optical path long enough to contribute
to the signal than is the case for a flame atomizer
261) With this understanding we can ask why the hollow cathode lamp has a low
pressure of argon filler gas.
The pressure of the argon is low to minimize collisions of argon atoms
with sputtered atoms. Collisions of excited state sputtered atoms with
argon atoms will lead to broadening of the output of the hollow cathode
lamp and potentially lead to the same problem described above with the
use of a continuum source. A low pressure of argon in the lamp insures
that the line width from the hollow cathode lamp is less than the line
width of the absorbing species.
CHECK POINT 04-03
1) In Flame emission photometers, the measurement of _____________ is used for
qualitative analysis
2) Which of the following is not an advantage of Laminar flow burner used in Flame
photometry?
SUMMARY
While other analytical techniques may offer specific advantages ov er atomic absorption, it
can be seen from the above comparison that no single technique offers all of the
advantages. The versatility, moderate cost, and established methodology of atomic
absorption will continue to make it a valuable tool for the laborato ry.
KEY WORDS
Inductively coupled plasma mass spectrometry; sample introduction; total element
quantitation; element speciation; species identification
REFERENCES
Benue, Makurdi, Nigeria. International Journal of Environment and Bioenergy 8:56 -67.
contents in samples of different medicinal plants. International Journal of Chemical Science
9(3):1126-1132.

1) Colour
2) Sample containing two or more solvents can be burned efficiently
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=XKx9XSwTUsY
https://www.youtube.com/watch?v=F-_fR2cqQ4g
WIKIPEDIA
https://www.priyamstudycentre.com/2021/11/atomic-absorption-spectroscopy.html

https://www.iitk.ac.in/che/PG_research_lab/pdf/resou rces/AAS-GTA-reading-
material.pdf
OER
____
REFERENCE BOOKS
3) Deewan SK. Organic spectroscopy (N.M.R., I.R., Mass and UV).New Delhi:CBS
4) William K. Organic Spectroscopy. Macmillan: Macmillan Chemistry Text; 1991.
5) Beckett AH, Stenlake JB. Practical Pharmaceutical Chemistry: Part -II. London:The
6) Verma RM, Analytical Chemistry:Theory and Practice. Third Edition. New Delhi: CBS
7) Ravi Sankar S., Text Book of Pharmaceutical Analysis, Tiruneliveli:Rx Publications:
2006.

CREDIT 04-UNIT 04: INDUCTIVELY COUPLED PLASMA
SPECTROSCOPY:
LEARNING OBJECTIVES
 State the different forms of plasma sources available.
 Explain the principle of operation of each plasma source.
 Explain the concept of temperature in relation to plasmas.
 Explain the role each plasma source has in atomic spectroscopy.
INTRODUCTION
Greenfield et al. developed plasma-based instruments in the mid 1960s about the same time
flame-based instruments such as FAAS and FAES became prominent (Analyst, 89, 713-
720, 1964). These first plasma-based instruments used direct current (DC) and microwave -
induced (MI) systems to generate the plasma. Interference effects and plasma instability
limited the utility of plasma instruments during analysis; consequently flame -based
spectrometry instruments (such as FAAS) dominated the analytical market for metals
analysis and remain effective today.
The limitations of the first plasma instruments were overcome by utilizing an inductively
coupled plasma (ICP) instead of DC or MI generated plasma. ICP optical systems became
popular in the 1980s due to their decreased cos t, lower time investment during analysis, and
labor saving advantages. FAAS instruments require a unique radiation source (lamp) for the
approximately 35 elements they can measure. Because the lamp must be changed between
each element of interest, FAAS (and FAES) techniques analyze a single element at a time
and are unable to easily analyze metalloids. ICP optical systems, by contrast, can analyze
about 60 different elements at the same time with a single source (the plasma). The most
common instruments today are inductively coupled plasma—atomic emission spectrometers
(ICP-AES) and inductively coupled plasma—mass spectrometers (ICP-MS). ICP-AES will
be discussed in this chapter while ICP-MS will be the subject of the next chapter.
04-04-01: ATOMIC EMISSION SPECTROMETRY THEORY
The operation of an ICP-AES system relies upon the same interaction of molecules with
electromagnetic radiation.The two emission systems, FAES and ICP -AES, differ in the way

atomic species are created and excited. Because of the relativ ely low temperatures (~2000-
2500 C) in a flame-based system, not all of the atoms or elements present in the sample are
excited, particularly if they exist in a polyatomic compound. Some elements readily form
non-emitting and refractory oxides that result in an underestimation of their concentration.
In plasma-based systems the temperature is considerably hotter (~10 000 K for Ar ICP) that
results in more effective excitation of atoms (generally greater then 90%) of approximately
60 elements including some nonmetals. This intense heat prevents polyatomic species from
forming, thus increasing the detection limits for many elements. Atoms are excited, and in
many cases ionized, by the intense heat of the plasma, and the emission of a photon occurs
via resonance fluorescence (normal valance electron relaxation by photon emission). While
plasma-based systems eliminate many problems, they are not free of interferences due to
the excitation and subsequent emission of spectral lines for every element in the sample a s
well as the Ar added to facilitate plasma generation. The spectral overlay that results from
these possible emissions is overcome in modern instruments with specialized sequential
monochromators (Section 4.4.4). ICP-AES, compared to FAAS/FAES, offers high
selectivity between elements, high sensitivity, a large dynamic range, especially as
compared to FAAS that is limited by Beer’s law, lower detection limits, multi -element
detection, and fewer matrix interferences.
Components of Inductively Coupled Plasma—Atomic Emission Spectrometry System (ICP-
AES):
1) Overview:
An ICP-AES system can be divided up into two basic parts; the inductively coupled plasma
source and the atomic emission spectrometry detector. Figure 4.1 shows the common
components of an ICP-AES system from the late 1980s to the 1990s. The inductively
coupled plasma source has mostly been unchanged since its invention with the exception of
innovation in monochromator type, which enables greater suppression of interference
phenomena. Modifications of this common system will be explained in the following
sections.
Sample solutions include digested soil or other solid material or natural water. Typically the
sample solution is acidified up to 2-3% in HNO3 to prevent adsorption of metals onto
polypropylene sample bottle or onto instrument tubing or glassware prior to introduction
into the plasma. In Figure 3-1, the sample is introduced to the nebulizer chamber via a
peristaltic pump and tygon tubing attached to an automatic sampler. A peristaltic pump
operates by sequentially compressing flexible tubing with evenly spaced and rotating
rollers that pull/push the liquid through the system. The rate of sample introduction into the
plasma changes as the rotation rate of the peristaltic rollers increases or decreases. Flow of
sample and Ar gas through the small aperture of the nebulizer creates very small droplets
that form a mist of µm-sized particles in the nebulizer chamber. Larger sample droplets

collect on the chamber walls and are removed through a dra in, while smaller particles travel
with the Ar flow and enter the torch. Evaporation, atomization, and excitations/ionizations
occur in the plasma at temperatures reaching 10,000 K. Ar not related to the sample is also
excited and ionized because this gas both carries the sample aerosol and confines the
location of the plasma to prevent damage to the rest of the instrument. As the
excited/ionized atoms leave the hot portion of the plasma, excited valence electrons relax
and emit a photon characteristic of the electron transition. This photon is specific to the
element but does not yield any information about the isotopic state of the element, unlike in
mass spectrometry Visible and UV radiation emitted from the sample constituents enters the
monochromator through a small slit where the wavelengths are separated by grating(s)
and/or prism(s) before being captured and measured by a wide variety of detectors.
Because spectral interferences may still occur, the choice and configuration of the
monochromators in the instrument is important and has been the target of innovation. In
Figure 4.1, the most common form of a monochromator (a Rowland circle) and detector
(photomultiplier; PMT) is shown: The Rowland system utilizes a concave Echellette -style
grating monochromator to separate the various emission lines and simultaneously focus
individual wavelengths on to a series of slits, with each slit aligned to allow a specific
wavelength of radiation to pass to a detector. The standard detector, a photomultiplier tube
(PMT), was discussed in Section 2.2.9. Some systems use multiple PMTs at fixed locations
to monitor each wavelength simultaneously (Figure 3 -1) whereas other systems use a single
PMT and move it to different locations to detect each wavelength. Data from the se
detectors are processed by a computer because multiple wavelengths are measured in an
ICP-AES system at the same time.

2 Sample Introduction and Optimization:
The predominate form of sample matrix in ICP -AES today is a liquid sample: acidified
water or solids digested into aqueous forms. Given the automated nature of the ICP
analysis, all modern systems are purchased with automatic samplers where a computer -
controlled robotic sampling arm takes liquids from each sample via a peristaltic pump from
plastic tubes located in specific locations in a sampling tray. Liquid samples are pumped
into the nebulizer and sample chamber via a peristaltic pump as shown below. Then the
samples pass through a nebulizer that creates a fine mist of liquid particles. Large r water
droplets condense on the sides of the spray chamber and are removed via the drain (pumped
out of the chamber also by the same peristaltic pump) while finer water droplets move with
the argon flow and enter the plasma. Nebulizers help ensure that th e sample enters into the
plasma at a uniform flow rate and specific droplet size. Droplets that are great than 5 µm in
diameter are likely to interfere with plasma stability.

Figure 4.2.An Overview of Sample Introduction and the Nebulizer Chamber. (The n ebulizer
shown here is a pneumatic style, described below.) While there are numerous types of
nebulizers for a variety of specific applications, the three most commonly types are the (1)
pneumatic, (2) ultrasonic, and (3) grid. Because argon is used in gen erating the plasma
(discussed below) it is most often used as the gas in these various nebulizers, but other
gases can be used. The most common pneumatic nebulizer for samples containing low
concentrations of total dissolved solids is the concentric nebuli zer shown in Figure 4.3, but
higher suspended solids and dissolved solids samples are commonly introduced to the
plasma via the Babington nebulizer.

Ultrasonic nebulizers are used to provide more sample delivery to the plasma and thus
improve detection limits. An ultrasonic generator surface, usually a piezoelectric crystal
that rapidly vibrates to generate sonic energy, is used to create extremely fine droplets that,
at low flow rates, are completely transferred to the plasma (unlike considerably lower
efficiencies from pneumatic nebulizers). Grid nebulizers create a fine mist by placing a grid
in front of the argon flow. The liquid sample is allowed to flow down the grid and as argon
passes through the grid it creates fine droplets. Again, the most com mon commercially
available nebulizers use the pneumatic design.
ICP systems have a few sample requirements or limitations. Micrometersized particles must
be removed by filtration or centrifuge or dissolved prior to introduction to a sample vial
because the particles can easily clog the tip of the nebulizer. A clogged tip will not be
automatically detected by the instrument, but will be detected by a trained operator by the
absence of any sample, internal standard, or standard analyte concentrations in the f inal.
Another limitation of the nebulizer is the presence of high total dissolved solids (TDS) that
will eventually cause the accumulation of solids in the tip of the nebulizer, as well as in the
sample chamber and on the sampler cones located just after t he plasma (in ICP-MS
instruments only). Most ICP instruments limit the sample TDS level to approximately 0.1 to
0.2 percent salts by weight. Higher salt contents can enhance atomization and ionization of
some elements and suppress or interfere with others (Walsh, 1997). Likewise, the acid
concentration of liquids entering the plasma should be limited to approximately two to
three percent for nitric and hydrochloric acid. Rarely hydrofluoric acid may be used if a
particularly refractory element is of interest, but then the acid concentrations are less than
0.5% because it will degrade the quartz torch with time. Some samples, such as food -based
beverages or plant extracts, can contain high concentrations of organic matter. It is best to
oxidize this organic matter in an acid or peroxide digestion prior to analysis since carbon

will rapidly accumulate on the components of the instrument if high organic matter
containing samples are directly injected into the plasma. This carbon can reduce sample
flow and capture elements and ions as the carbon builds up, specifically at the cone
apertures that facilitate the transition from ambient pressure in the plasma region to the
high vacuum detector region (in ICP-MS systems). When a portion of a carbon plaque drops
back into the analytical stream, an anomalously high, and false, measurement can occur.
Other forms of sample introduction are used but are not as common as liquid injection.
These include (1) direct insertion of 10-30 mg of sample on a graphite probe into the
plasma via the normal nebulizer entry port, (2) the injection of the effluent from
chromatographic separation systems, especially from high performance liquid
chromatography (HPLC), supercritical chromatography, and ion chromatography (IC) units
where compounds containing elemental analytes of interest are first separated by
chromatography and then introduced into the plasma for elemental analysis, (3) where the
cold vapor techniques described in Section 3.4 for mercury analysis is connected to
the plasma inlet via the nebulizer port, and (4) where the hydride generation system from
Section 3.4 for selected metals can also be connected to the nebulizer port.
SOLVED PROBLEMS 01
262) Ionization of analyte atoms in flame/plasma can be suppressed by:
a. EDTA or other complexing agentsb. Addition of KCl to the matrix c. Addition
of oxyanions such as sulfate or phosphate. d. Internal standards methods.
263) Because of the mulit-element capability and atomization / temperature sensitivity of
emission intensity, the following analytical method has proved highly successful in
ICP-AES:
a. Standard additions b. Internal standards c. D 2 background correction d. nonlinear
calibration analysis
264) which Inductively coupled plasma torch with laminar flow cooling
An improved inductively coupled gas plasma torch. The torch includes
inner and outer quartz sleeves and tubular insert snugly fitted between
the sleeves. The insert includes outwardly opening longitudinal channels.
Gas flowing through the channels of the insert emerges in a laminar flow
along the inside surface of the outer sleeve, in the zone
of plasma heating. The laminar flow cools the outer sleeve and enables
the torch to operate at lower electrical power and gas consumption levels
additionally, the laminar flow reduces noise levels in spectroscopic
measurements of the gaseous plasma.
265) High voltage AC plasma torches with long electric arcs for plasma-chemical
applications
Powerful AC plasma torches are in demand for a number of
advanced plasma chemical applications, they can provide high enthalpy
of the working gas. IEE RAS specialists have developed a number of
models of stationary thermal plasma torches for continuous operation

on air with the power from 5 to 500 kW, and on mixture of H2O, CO2
and CH4 up to 150 kW. AC plasma torches were tested on the pilot
plasmachemical installations. Powerful AC plasma torch with hollow
electrodes and the gas vortex stabilization of arc in cylindrical
channels and its operation characteristics are presented. Lifetime of its
continuous operation on air is 2000 hours and thermal efficiency is
about 92%, the electric arc length between two electrodes of
the plasma torch exceeds 2 m.
266) Approximately how many elements can ICP -AES or ICP-MS be used to analyze?
267) Why can ICP be used to analyze more elements than FAES?
04-04-02: THE INDUCTIVELY COUPLED PLASMA TORCH

The torch unit of an ICP is used to create and sustain a plasma. A plasma is an electrically
conducting gaseous mixture containing enough cations and electrons (though the plasma
has a neutral charge overall) to maintain the conductance. One common example of a
simple plasma is a regular flame which will conduct an electrical current across it; cations
and electrons are created upon ignition of the fuel and travel upward in the flame until they
are cooled above the flame. Another common plasma is used in scanning electron
microscopy (SEM) where a sample is coated with graphite or a metal in a vacuum chamber
in order to make the surface conductive (a standard requirement for obtaining high quality
images). DC arc and microwave plasmas can also be used to generate plasmas, but f or
purposes of metal analysis, the inductively coupled plasma system described below is most
important. The purpose of the torch is to (1) evaporate the solvent (usually water) from the
analyte salts, (2) atomize the atoms in the salt (break the ionic bond s and form gaseous
state atoms), and (3) excite or ionize the atoms. In the case of ICPAES, only excitation is
needed as in FAES but given the extreme temperatures (up to 10 000 K) of the argon plasma
used in modern ICP systems, the excitation of atoms is virtually complete for most
elements.A modern torch system is illustrated in Animations 4.1 and 4.2. The torch
described here is composed of three concentric quartz tubes. The samples and the argon gas
used to aspirate it pass through the center tube. The plasma generating gas (argon) passes
through the middle tube, and the argon passing through the outer tube is used to cool the
quartz torch.
The plasma is sustained by a radio-frequency generator that creates an oscillating magnetic
field around the torch that results in ohmic (inductive) heating of the charged gases at the
end of the torch. Ohmic heating occurs when an electrical current is passed through a
conductor, that in turn, creates more heat. Three types of radio -frequency generators have
been used. Older types are based on piezoelectric crystal oscillators and “free -running”
generators in which the oscillation is set according to the combinations of the components
of the circuit; examples include the Armstrong, Hartley, Colpitts, and tuned -anodetuned
gate oscillator electronic circuits. Most modern analytical ICP systems use solid -state

semiconductor generators where the circuit consists of (1) a capacitor used to store a high
electrical charge (thus requiring the 220 -240 V electrical power requirements) and (2) an
inductor coil to deliver the oscillating current to the torch and generate the magnetic field
around the torch. The capacitor is hidden from view in ICP systems and buried in the
electronics of the instrument. The inductor coil is visible and is the approximately 3-mm
hollow copper coil wrapped three times around the end of the torch. The capacitor
responsible for generating the plasma from argon gas, oscillates an electrical field at a rate
between approximately 27 and 41 MHz (a frequency regulated by the FCC) and through
induction creates a magnetic field in the plasma. The intensity of the frequency, measured
in Watts, is sufficient to promote the valance electrons in some of the Ar atoms but not
ionize them sufficiently to initiate or sustain a plasma. The creation of plasma occurs when
a spark (from a Tesla coil; basically an automatic gas grill lighter) introduces free electrons
at the end of the torch when the electrical field is being oscillated at a specific frequency by
a RF generator. The seed electrons from the Tesla coil oscillate in an angular path and
periodically collide with argon gas atoms and ionize them, releasing more electrons. Due to
their kinetic energy and collisions with other atoms a large amount of heat is generated ,
enough to generate and sustain a plasma at temperatures up to 10,000 K. In terms of an
electrical analogy, the term “inductively coupled” in ICP is a result of the coupling of the
induction coil and the electrons. The copper induction coil serves as the “primary winding”
of the radio-frequency transformer and the “secondary winding” is the oscillating electrons
and cations in the plasma; the two “windings” are thus coupled together because the second
winding depends on the presence of the first The RF gen erator also contains a feed back
loop where the interaction of the electronic/magnetic field in the capacitor/induction coil is
monitored. If the flow rate of argon gas is too low or if small amounts of O2 or high
amounts of water vapor are present in the torch during the initiation of the plasma, the RF
generator will sense their presence by a change in the feedback between the oscillation and
the RF generator. When this happens, the RF generator shuts down to protect the electronics
in the system from overheating. Thus, atmospheric O2 cannot be present in the Ar and the
flow rate of nebulizer sample (water) must also be controlled to successfully light the torch.
The process of lighting the plasma is visualized in Animation 4.1
In this animation the argon is turned on and the pressures are allowed to equilibrate without
the introduction of any sample or blank solutions to the nebulizer. The radiofrequency
generator then ramps the wattage through a series of cycles. A typical ramp cycle begins by
turning the RF generator to 200 Watts. Subsequently the electronics go through a
preliminary check that adjusts the electronics and minimizes the resistance between the RF
generator and the induction coil. Next the RF wattage is ramped to 900 W where excitation
of valence electrons in some Ar atoms occurs and the Tesla coil initiates the excitation and
ionization of Ar atoms and the plasma is lit. The circulation of electrons and Ar cations in

close association results in ohmic heating that generates more electrons, c ollisions between
Ar atoms, and an increase in temperature. The wattage is then increased to 1200 and the
resistance is minimized again via electronic adjustments. Finally the wattage is adjusted to
the suggested energy level for the elements of interest; this is usually between 1250 and
1550 W. Please review Animation 4.1 on the book’s web site at this time.
If the region of ohmic heating is not controlled, the plasma would continue to heat until it
melted the quartz torch (and the other components of th e ICP spectrometer). The torch is
cooled in two ways, the first is by the tangential introduction of relatively large volumes of
argon gas through the outer tube of the torch. This argon flow spirals around the middle
tube resulting in uniform cooling. Furthermore cooled water flows through the copper
induction coil of the RF generator that is wrapped around the end of the torch. These
combined cooling systems promote an equilibrium maximum temperature of approximately
10 000 K in the hottest portion of the plasma. The portion of the plasma that ICP -AES
measurements are concerned with is about 5000 -6000 K and is located in coneshaped region
outside the quartz torch.
After successful ignition of the torch, samples are introduced into the system through the
nebulizer (Animation 4.2). Upon entry into the plasma, the solvent evaporate and salts
form. Then, these compounds decompose as they move farther into the hotter portions of
the plasma. Next, the valence electrons on the analyte atoms are excited (for ICP -AES
measurements) or completely removed (ionized for ICP -MS measurements). The intense
heat that sample molecules encounter in the plasma is sufficient to decompose most
refractory compounds, thus only atoms or atomic ions are present in the plasma (Section

4.4). This heat also causes complete excitation of atoms and leads to higher detection
limits, compared to FAES where the extent of excitation is elementand flame temperature -
dependent. In ICP-AES, as the atoms exit the plasma and cool to approximately 600 0 K,
they relax and emit a characteristic photon that enters one of the monochromator/detector
systems described in the next section. In ICP -MS (Chapter 4), the plasma enters a vacuum
chamber where the cations are separated by a mass filter (mass analyzer) and detected by a
specialized photomultiplier tube. An illustration of the drying, atomization, and excitation
and ionization is shown in Animation 4.2.
Animation 4.2. Animation of Sample Introduction and the Subsequent Reactions in the
Torch of an ICP System. Note that this animation is a simplistic illustration of a complex
process and water molecules do not actually remain intact at 10,000 o K. Charge transfer to
the cations actually occurs due to Rayleigh explosion.
The consumption rate of Ar gas is an important issue and accounts for most of the
operational costs of an ICP. Older systems can use up to 20 L/minute, while modern
systems have reduced the flow to below 10 L/minute. Systems are being designed that are
portable and use far smaller flow rates of Ar gas. Many laboratories use cryogenic sources
of Ar to reduce operational costs. Current prices for liquid Ar (equivalent to approximately
5000 cubic feet at STP) are approximately $325, whereas the cost of three T-size cylinders
of gaseous Ar (equivalent to approximately 334 cubic feet at STP) is approximately $420.
Thus, use of a cryogenic tank is far more economical than individual gas cylinders. Gases
generated from a cryogenic tank are often more pure than those obtained from a standard T-
sized gas cylinder.
Around 2005, a new version of ICP-AES was introduced to the market based on
microwave-induced N2 plasma. A major advantage of this system is that it uses atmospheric
N2 to generate the plasma and greatly saves on cryogen costs by using a rel atively
inexpensive, built in nitrogen generator. One slight limitation of the system is the lower

plasma temperature, ~5,000K, that results in relatively lower detection limits, comparable
to FAAS detection limits, but lower then Ar-based ICP-AES systems.
SOLVED PROBLEMS 02
268) Which of the following statements is not true about amorphous solids? a ) They are
anisotropic in nature b) On heating they may become crystalline on certain
temperature c) They may become crystalline on keeping for long time d) Amorphou s
solids can be moulded by heating
269) What type of solid ‘quartz’ is ? a) Molecular solid b) Covalent solid c) Ionic solid d)
Metallic solid

270) Atomic absorption spectrometry
a. Principles of FAAS – where selectivity and sensitivity arise b. Spectrometer design c.

Atomization processes d. Sensitvitiy and atomization: protecting agents, releasing
agents, radiation buffers e. Bandwidth considerations and calibration curve linearity.
271) Formation of oxides or molecular species in flame/plasma can be suppressed by:
EDTA or other complexing agentsb. Addition of KCl to the matrix c. Addition of

oxyanions such as sulfate or phosphate. d. Standard additions methods
272) Approximately how many elements can FAAS be used to analyze?
273) Why is acid added to all samples during sampling or for sample digestion in FAAS,
FAES, and ICP analysis?
04-04-03: SEPARATION AND DETECTION

After the atoms are excited or ionized in the plasma, they exit the high temperature region
and electronically relax. This results in the emission of at least one element-specific photon
available for detection. The first choice to bemade by the analyst is the position of the
monochromator entrance relative to the plasma source. Two choices are available, axial and
radial alignment. A radial design allows photons to move from the side of the plasma (at the
end of the torch) to the entrance slit while an axial design gives higher intensities (and
better detection limits) since the photons come from the center and end of the plasma. Thus,
depending on the concentration of analytes in a given sample, the analyst may choose to
monitor the emissions from the radial angle for higher concentrations; this avoids burning
out the detector, which is costly to replace. Or the analyst may choose to use th e axial
monochromator alignment for lower concentration samples. Changing the angle of
observation can potentially avoid additional sample preparation such as dilutions. Many

brands of instruments allow a selection between radial and axial monitoring Three broad
categories of detection are available for analyzing the emitted photons: sequential,
simultaneous multi-channel, and Fourier transform systems. In the first two, all
wavelengths enter a monochromator where they are dispersed by prisms and/or grating
monochromators and are then transmitted to the detector (most commonly the PMT
presented in Animation 3.4, or a CCD presented in Figure 3.9). Fourier transform systems
produce spectral separations by capitalizing on constructive interference techniques as first
developed for Michelson’s interferometer in 1881. In Fourier transform systems, no slits or
monochromators are required, and this creates better detector limits because more intense
radiation reaches the detector. Fourier transform systems also have higher spectral
resolution (and thus have fewer spectral interferences) and can simultaneous monitor all
wavelengths for longer times. This text will only cover sequential and simultaneous multi -
channel systems that use monochromators because Fourier tran sform systems extend past
the basic ICP instrumentation goal of this eTextbook and are considered “higher end”
systems.
The first ICP-AES systems used a sequential mono chromator to separate the analyte -
emitted photons by wavelength before detecting them w ith a single detector. This approach
is analogous to the FAES system where only one element could be analyzed at a time. In a
sequential system, if a sample needed to be analyzed for multiple elements, the grating
system was rotated to direct the appropriate wavelength to the exit slit of the
monochromator and into a PMT. While ICP-AES provided superior detection limits
compared to FAES instruments, it was just as slow and labor intensive as FAES.
Simultaneous multi-channel systems rapidly became economical as component production
costs decreased and as labor costs have increased with time. In these systems, multiple
elements can be detected at the same time using one of two designs. One way is to use a
standard grating monochromator that separates the photo ns based on wavelength and directs
the photons of interest to specific exit slits. Then, a single detector was rapidly moved from
one slit to the other to analyze photons of various wavelengths. This type of system is
shown Figure 4.6. Another way to accomplish multiple element detection is by placing an
individual detector, again usually a PMT, at each exit slit. Such a system, the Rowland
circle, was shown in Figure 4.1 and is shown again here as Figure 4.7. The Rowland design
increases the upfront cost of an instrument and the running cost as PMT are replaced but
this design significantly decreases the analysis time.

Some instruments use one detector for UV wavelengths and another for visible
wavelengths. There are a variety of designs for these la tter systems illustrated below. These
more advanced instruments have an increased cost but are more economical recently due to
decrease in the production costs of CCDs and CIDs versus PMTs. They also significantly
reduce the lab bench space requirements. Instruments such as the one in illustrated in
Figure 4.9 (1) offer superior resolution compared to a Rowland circle due to the advance
monochromator systems, (2) offer the immediate option to monitor secondary or greater
diffraction that can be used in high concentration samples, (3) reduce the size of the
instrument due to the reduced size of the detector(s), and (4) offer more inexpensive
instruments as the cost of CCDs and CIDs become more economical.

Data Collection:
When single element detection was the goal of instrumentation, a simple chart recorder or
digital display was sufficient for data collection. However, with the advances in ICP -AES
technology today, computers are a necessity, not only to control the automatic sampler and
the instrument control but also for data collection. Data collection systems are divided into
a “method file” to run the instrument and “sequence file” to tell the instrument where a
sample is in the sample tray, when to run it, and where to store the collected data file.
SOLVED PROBLEMS 03
274) During the formation of a solid, (a) Some energy is lost (b) some energy is gained (c)
Energy remains constant (d) some energy may be gained or lost depending on the
system Ans: (a)
275) Which of the following techniques is not a resonance based technique?
Fluorescence, NMR, EPR
276) Strengths and weaknesses of ICP-AES and ICP-MS
Both systems are rather inefficient, with ICP -AES being extraordinarily so. (2)
ICP-AES signal levels are only a factor of two or so weaker than th ose in ICP-MS.
Introduction – A Forward-Looking Perspective (3) Background levels in ICP -MS
are far lower than those in ICP-AES. (4) Signal and noise characteristics are all
highly dependent on instrumentation and therefore should be able to be controlled .

277) How to make Nanopillars stable during ICP Plasma Etching?
I have an issue going with my fabrication process for etching the BARC (bottom
anti reflective coating) with O2 plasma in ICP. I am using Interference
Lithography to pattern 2D nanopillars using positive photoresist. I am able to
define the pillars well using right thickness of BARC and the aspect ratio is <1:3
which technically is good to process. The issue arises when BARC starts to etch .
The pillars fall down in <10s of etching time whereas 45s of etching time is
required to etch BARC completely.
278) Which parameters are involved in calculating effective force in plasma?
279) Why is plasma better than flame?
280) Which gas is used in ICP-AES?
04-04-04: INTERFERENCES:
ICP systems greatly reduce the number of interferences over those created in flame -based
systems. Nebulizer, chemical, ionization, and spectral interferences are all present in ICP
systems, but spectral interferences are most prominent. Nebulizer interferences (also known
as matrix effects) can arise from physical and chemical differences between referen ce
standards and samples, or between samples, such as the inconsistence presence of matrix
salts and organic compounds or different viscosities and surface tension of the liquid. Each
of these can be overcome by the use of standard addition calibration tec hniques discussed
in Chapter 1, but at a significant increase in the cost of analysis (primarily due to labor
costs). For low ionic strength samples, nebulizer interferences are less prominent. Chemical
interferences are common in FAAS and FAES but are les s common or practically
nonexistent in ICP-AES due to the relatively high temperature of the plasma, long residence
time in the plasma, and inert atmosphere of the Ar plasma. Ionization interferences, in
direct arc- and microwave-produced plasmas, usually only occur for easily ionized elements
such as alkali and alkaline earth elements. The net result of ionization interferences is an
increase or decrease in the intensity of emission lines for these elements. Few ionization
interferences occur for these elements in ICPAES.
Spectral interferences can be common in high temperature plasmas as opposed to flame -
based systems given the complete excitation and subsequent emission of all compounds in

the sample (including the argon). Spectral interferences can be di vided into three different
classes. The first type is spectral line coincidence when resolution of the mo nochromator of
the system is too poor to separate the analyte line from a matrix line. The use of Echelle
monochromators with higher resolution elimina tes spectral interferences. The second cause
of interferences occurs when a wavelength of interest overlaps completely with a nearby
“broadened line wing”. This can be solved by monitoring a secondary emission line for that
particular element. Most instruments use a background correction technique to overcome
this type of interference. The final type of spectra interference referred to as spectral
continuum occurs when stray light results from the recombination of electrons with Ar ions
in the plasma that emits multiple intense lines. This can be avoided in some instruments by
adjusting the temperature of the plasma or monitoring alternate lines. Stray light from
matrix emissions can be avoided by use of highend optical components such as “solar -blind
PMTs”.
Applications:
1) Agricultural and Foods:
• The ICP-OES technique has been applied to the analysis of a large variety of
agricultural and food materials. Types of samples include soils, fertilizers,
plant materials, feedstuffs, foods, animal tissues, and body fluids. Analysis
of infant formula for Ca, Cu, Fe, Mg, Mn, P, K, Na and Zn;
• Determination of trace metals in beer and wine.
2) Biological and Clinical:
• The use of surgical equipment, such as scalpels, needles, scissors, and
forceps, often contaminates the sample with trace quantities of the very
elements being determined in the sample.
• • Determinations of Cr, Ni and Cu in urine. • Determination of Al in blood. •
Determination of Cu in brain tissue. • Determination of Se in liver. •
Determination of Ni in breast milk. • Determination of B, P and S in bone. •
Determination of trace elements in oyster and tuna tissues.
3) Geological:
• Determination of major, minor and trace compositions of various rocks,
soils, sediments, and related materials.
• The major use of ICP-OES in this field is mainly used for prospecting
purposes. • The technique is also used for applications such as determining
origins of rock formations and for marine geochemistry. • Determination of
U in ore grade material. • Analysis of river sediments for several metals. •
Analysis of carbonate drill cores for major, minor and trace elements. •
Determination of rare earth elements in rock formations. • Analysis of
plankton for several elements.

4) Environmental and Waters:
• Analyses of sewage sludge, domestic and industrial refuge, coal and coal fly
ash, and dust and other airborne particulates. • Various water quality
analyses as required by the U.S. Environmental Protection Agency. •
Determination of Fe, Cd, Cu, Mo, Ni, V, and Zn in seawater. • Determination
of phosphorus in municipal wastewater. • Determination of heavy metals in
inner-city dust samples. • Trace metal analysis of coal fly ash.
5) ) Metals:
• Determination of toxic, trace and major constituents in coal and slags. •

Analysis of low alloy steels for As, B, Bi, Ce, La, P, Sn and Ta; high-
precision determination of Si in steels; • Determination of contaminants in
high-purity Al. • Analysis of superconducting materials for trace
contaminants.
6) Organics: • Analysis of organic solutions by ICP -OES is important not only for
analyzing organic-based materials such as petroleum products but also for a wide
variety of other applications. • The analysis of used lubricating oils for trace metal
content is one of the more popular applications for organics analy sis by ICP-OES. Some
other applications include analysis of solvent -extracted geological materials for trace
elemental composition. • Determination of lead in gasoline; • Determination of Cu, Fe,
Ni, P, Si and V in cooking oils. • Analysis of organophospha tes for trace contaminants. •
Determination of major and trace elements in antifreeze.
SOLVED PROBLEMS 04
281) What is meant by the term 'hard ionization'?
An ionization technique which involves electrons impacting the
analyte molecule.
An ionization technique transferring a relatively large amount
of energy to the analyte.
An ionization technique transferring very little energy to the
analyte
An ionization technique which forms many fragment ions.
282) What is the typical energy of the electrons used to ionize analytes by Electron
Ionization (EI)?
50 eV
70 eV
1 eV
1000 eV
283) What exposure time and number of average for multichannel spectrometers?

284) How to estimate dust debye shielding length.
285) Quadrupole Ion Deflector.
Quadrupole Ion Deflector (QID) is an electrostatic analyzer that turns
the analyte ion beam 90°. A software -controlled scanning voltage is
applied to the QID to enhance the transmission of selected ions into the
first Transmission Analyzer Quadrupole , thereby improving sensitivity
and eliminating the transmission of photons and neutral species to the
mass spectrometer via the vacuum.
286) Inductively-coupled plasma ion source
The ICP is maintained by a radiofrequency power generator that is
coupled into the discharge using a water-cooled metal load coil. The
ICP is housed within a quartz ‘torch’ that allows for Ar to enter the
discharge in three ways, 1) through the main -volume of the torch to
maintain the ICP discharge, 2) along the sides of the inner walls of the
torch to prevent melting, and 3) through the central c hannel to
introduce sample to the ICP.
287) List and explain the types of interferences in ICP -AES.
288) Why is a molecular oxygen band not observed in an emission spectrum of air
discharge?
CHECK POINT 04-04
1) Double focussing section analysers offer better resoluti on than ICP
spectrometry system
2) The most common type of ion detector found in ICP system is which of the
following?
SUMMARY
Optical spectrometry has made considerable advances since the first flame -based
instruments were introduced in the 1960s. Recent advances in plasma technology,
monochromator layout, and computer-based detector systems such as charge transfer
devices have given a new meaning to “state-ofthe-art” technology. Today, low-end FAAS
instruments are only used in situations where only one or tw o elements are analyzed
infrequently. High sample throughput situations, such as those found in industry and
environmental monitoring, require automated systems that can perform multiple analyses in
a minimum amount of time. But these demands are paid for with instruments of
significantly higher cost. While ICP-AES detection limits are significantly better than
flame-based techniques, mass spectrometry yields even better detection limits and can
distinguish between different isotopes.
KEY WORDS
Emission line intensity, population distribution, ionizing plasma, recombining plasma,
ionization balance, radiation transport, dense plasma.
REFERENCES
[1] Griem H R 1964 Plasma Spectroscopy (New York: McGraw -Hill) [2] Lochte-Holtgreven
W 1968 Plasma Diagnostics (Amsterdam: North-Holland) [3] Griem H R 1997 Principles of

Plasma Spectroscopy (Cambridge: Cambridge University Press) [4] Thorne A, Litzen U and
Johansson S 1999 Spectrophysics: Principles and Applications (Berlin: Springer) [5]
Fujimoto T 2004 Plasma Spectroscopy (Oxford: Clarendon) [6] Chen F F and Chang J P
2003 Lecture Notes on Principles of Plasma Processing (New York: Kluwer) [7] Hippler R,
Pfau S, Schmidt M and Schoenbach K H eds 2001 Low Temperature Plasma Physics
(Berlin: Wiley) [8] Huddlestone R H and Leonard S L 1965 Plasma Diagnostic Techniques
(New York: Academic) [9] Hutchinson I H 1987 Principles of Plasma Diagnostics
(Cambridge: Cambridge University Press) [10] Auciello O and Flamm D C 1989 Plasma
Diagnostics Vol. 1 (San Diego: Academic) [11] Dean J R 1997 Atomic Absorption and
Plasma Spectroscopy
1) False
2) Channeltron
MOOCS
____
YOUTUBE VIDEOS
https://www.youtube.com/watch?v=InFhIHPZYIc
https://www.youtube.com/watch?v=mLazX_2atmM
WIKIPEDIA
https://en.wikipedia.org/wiki/Inductively_coupled_plasma_mass_spectrome try
https://en.wikipedia.org/wiki/Nebulizer
OER
____
REFERENCE BOOKS
S.N. Rarnan, D.F. Paul, J.S. Hamrnond, and K.D. Bomben, Microscopy Today, 2011, 19,
12-15.
S. Tougaard (2009) Quantification of Surface and Near-Surface Cornposition by AES and
XPS, in Handbook of Surface and Interface Analysis Methods for Problem -Solving, Second
Edition (eds J. Rividre and S. Myka), CRC Press, Boca Raton, Florida
V. Young and G. Hoflund (2009) Photoelectron Spectro scopy (XPS and UPS), Auger
Electron Spectroscopy (AE), and lon Scattering Spectroscopy (ISS), in Handbook of
Surface and Interface Analysis Methods for Problem-Solving, Second Edition (eds J.
Rividre and S. Myhra), CRC Press, Boca Raton, Florida.
N. Tumer (1997) X-ray Photoelectron Spectroscopy and Auger Electron Spectroscopy, in
Analyical Instrumentation Handbook, Second Edition (ed G. Ewing), Marcel Dekker, Inc,
New York, New York.

School of Architecture Science and Technology
Yashwantrao Chavan Maharashtra Open University, Nashik – 422222
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YASHWANTRAO CHAVAN MAHARASHTRA OPEN UNIVERSITY

V154: M.Sc. Chemistry

Foreword By The Director ................................................................................................... 4

Credit 03 ........................................................................................................................... 208

Credit 04 ........................................................................................................................... 280

Feedback Sheet for the Student ........................................................................................ 370

CHE506: Physical Methods In Chemistry Page 1

Dr. AmolKategaonkar Dr. Bharat More

This work by YCMOU is licensed under a Creative Commons Attribution-Non

 Book Publication : 31-October-2022 Publication No:2561

CHE506: Physical Methods In Chemistry Page 2

CHE506: Physical Methods In Chemistry Page 3

- Dr. Sunanda More

CHE506: Physical Methods In Chemistry Page 4

CHE506: Physical Methods In Chemistry Page 5

Introduction UV spectroscopy is type of absorption spectroscopy in which light of ultra -

CHE506: Physical Methods In Chemistry Page 6

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Various UV radiation sources are as follows

d. Xenon discharge lamp

e. Mercury arc lamp

Various Visible radiation sources are as follows

b. Mercury vapour lamp

All monochromators contain the following component parts;

• A dispersing device (a prism or a grating)

Polychromatic radiation (radiation of more than one wavelength) e nters the

3. sample containers or sample cells:

a) the path length, shape, size

b) the transmission characteristics at the desired wavelength

CHE506: Physical Methods In Chemistry Page 8

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CHE506: Physical Methods In Chemistry Page 10

CHE506: Physical Methods In Chemistry Page 11

λmax = Base value + Σ Substituent Contributions + Σ Other Contributions

CHE506: Physical Methods In Chemistry Page 12

1. In example 1, the double bond present within ring A is exocyclic to ring B as it

c) Endocyclic double bond:- Double bond present in a ring.

CHE506: Physical Methods In Chemistry Page 13

Exocyclic double bond = 1 x 5 = 5 nm

CHE506: Physical Methods In Chemistry Page 14

Base value =246 nm

CHE506: Physical Methods In Chemistry Page 15

CHE506: Physical Methods In Chemistry Page 16

CHE506: Physical Methods In Chemistry Page 17

2) There is a substance in a solution (4 moles/liter). The length of cuvette is 2 cm and

CHE506: Physical Methods In Chemistry Page 18

SHORT ANSWER QUESTIONS WITH MODEL ANSWER 01

01-01-02: ELECTRONIC TRANSITIONS:

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Factor affecting absorbance & intensity:

b) Effect of solvent: In polar solvent, 𝜋 − 𝜋 * transitions shift towards longer

CHE506: Physical Methods In Chemistry Page 23

CHE506: Physical Methods In Chemistry Page 24

Solution: Corrected absorbance= × 0 436 = 0 510

%𝑒𝑟𝑟𝑜𝑟 = × 100 = × 100 = 14 5%

SHORT ANSWER QUESTIONSWITH MODEL ANSWER 02

CHE506: Physical Methods In Chemistry Page 25

01-01-03: THE WOODWARD-FIESER RULES (CALCULATION OF 𝝀MAX (NM)

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In isomer A, due to steric hindrance, absorption shift towards lower wavelength.