Spectroscopy

Spectroscopy is the study of the absorption and emission of light and other radiation by matter.
Spectroscopy is a branch of science concerned with the spectra of electromagnetic radiation as
a function of its wavelength or frequency measured by spectrographic equipment, and other
techniques, in order to obtain information concerning the structure and properties of matter.
Spectral measurement devices are referred to as spectrometers.

Most spectroscopic analysis in the laboratory starts with a sample to be analyzed, then a light
source is chosen from any desired range of the light spectrum, then the light goes through the
sample to a dispersion array (diffraction grating instrument) and captured by a photodiode.

Atomic spectroscopy is the study of the electromagnetic radiation absorbed and emitted
by atoms. Since unique elements have unique emission spectra, atomic spectroscopy is applied
for determination of elemental compositions.

Electrons exist in energy levels (i.e. atomic orbitals) within an atom. Atomic orbitals are
quantized, meaning they exist as defined values instead of being continuous (see: atomic
orbitals). Electrons may move between orbitals, but in doing so they must absorb or emit
energy equal to the energy difference between their atom's specific quantized orbital energy
levels. In optical spectroscopy, energy absorbed to move an electron to a higher energy level
(higher orbital) and/or the energy emitted as the electron moves to a lower energy level is
absorbed or emitted in the form of photons (light particles). Because each element has a
unique number of electrons, an atom will absorb/release energy in a pattern unique to its
elemental identity (e.g. Ca, Na, etc.) and thus will absorb/emit photons in a correspondingly
unique pattern. The type of atoms present in a sample, or the amount of atoms present in a
sample can be deduced from measuring these changes in light wavelength and light intensity.

Molecular spectroscopy is the study of how molecules interact with electromagnetic radiation,
specifically by observing the wavelengths absorbed or emitted during transitions between
energy levels. This interaction reveals information about a molecule's structure, composition,
and energy levels. By analyzing the resulting spectra, it's possible to identify unknown
substances and determine their quantities.

Here's a more detailed explanation:

1. Interaction with Electromagnetic Radiation:

 Molecules have discrete energy levels (electronic, vibrational, and rotational).

  When electromagnetic radiation interacts with a molecule, it can cause the molecule to
transition between these energy levels.

 This interaction can involve the absorption of radiation (molecule gains energy),
emission of radiation (molecule loses energy), or both.

2. Molecular Spectra:

 The wavelengths of radiation absorbed or emitted during these transitions create a

unique pattern called a molecular spectrum.

 This spectrum acts as a "fingerprint" of the molecule, allowing for identification and
analysis.

3. Types of Molecular Spectroscopy:

 UV-Vis Spectroscopy:

Involves transitions between electronic energy levels, typically in the ultraviolet and visible
regions of the electromagnetic spectrum.

 Infrared (IR) Spectroscopy:

Studies vibrational modes of molecules, providing information about chemical bonds and
molecular structure.

 Raman Spectroscopy:

Similar to IR spectroscopy but relies on the scattering of light instead of absorption, also
providing information about molecular vibrations and structure.

 Nuclear Magnetic Resonance (NMR) Spectroscopy:

Explores the interactions of atomic nuclei with magnetic fields, providing detailed information
about molecular structure and dynamics.

 Fluorescence Spectroscopy:

Measures the emission of light after a molecule has absorbed light, often used for analysis of
molecules that are not directly detectable by absorption.

4. Applications:

 Material Science:
Identifying unknown substances, determining the composition of materials, and studying their
properties.

 Chemistry:

Analyzing chemical reactions, characterizing reaction products, and monitoring reaction

progress.

 Biology and Biochemistry:

Studying the structure and function of biological molecules, such as proteins and DNA.

 Environmental Science:

Analyzing pollutants and monitoring environmental conditions.

Electromagnetic radiation

Electromagnetic radiation is a form of energy that is produced by oscillating electric and

magnetic disturbance, or by the movement of electrically charged particles traveling through a
vacuum or matter. The electric and magnetic fields come at right angles to each other and
combined wave moves perpendicular to both magnetic and electric oscillating fields thus the
disturbance.

General Properties of all electromagnetic radiation:

1. Electromagnetic radiation can travel through empty space. Most other types of waves
must travel through some sort of substance. For example, sound waves need either a
gas, solid, or liquid to pass through in order to be heard.

2. The speed of light is always a constant. (Speed of light : 2.99792458 x 108 m s-1)

3. Wavelengths are measured between the distances of either crests or troughs. It is

usually characterized by the Greek symbol λλ.

Waves and their Characteristics

Amplitude

Amplitude is the distance from the maximum vertical displacement of the wave to the middle
of the wave. This measures the magnitude of oscillation of a particular wave. In short, the
amplitude is basically the height of the wave. Larger amplitude means higher energy and lower
amplitude means lower energy. Amplitude is important because it tells you the intensity or
brightness of a wave in comparison with other waves.
Wavelength

Wavelength (λ) is the distance of one full cycle of the oscillation. Longer wavelength waves such
as radio waves carry low energy; this is why we can listen to the radio without any harmful
consequences. Shorter wavelength waves such as x-rays carry higher energy that can be
hazardous to our health. Consequently lead aprons are worn to protect our bodies from
harmful radiation when we undergo x-rays. This wavelength frequently relationship is
characterized by: c=λν

where

 c is the speed of light,

 λ is wavelength, and

 ν is frequency.

Shorter wavelength means greater frequency, and greater frequency means higher energy.
Wavelengths are important in that they tell one what type of wave one is dealing with.

Frequency

Frequency is defined as the number of cycles per second, and is expressed as sec -1 or Hertz (Hz).
Frequency is directly proportional to energy and can be express as: E=hν

where

 E is energy,

 h is Planck's constant, (h= 6.62607 x 10-34 J), and

 ν is frequency.

Period

Period (T) is the amount of time a wave takes to travel one wavelength; it is measured in
seconds (s).

Velocity

The velocity of wave in general is expressed as:

For Electromagnetic wave, the velocity in vacuum is 2.99×108m/s2.

Electromagnetic spectrum

Fig.: Electromagnetic spectrum

2.1.2 Electromagnetic Spectrum
spectral regions can be given as follows (Fig. 2.3):
The characteristics of outer space and fall continuouslv
10 to infinity) originate from
1. Cosmic rays (v 3 x
earth due to their great penetrating power
by radioactive substances
2. y-rays [v 100 Hz(0.2 to 1)] emitted movement of electrons close to the
3. X-rays [v 10' Hz (1 to 10 ¢)l are emitted 'due to the
nuclei of relatively heavy atoms.
4. Ultraviolet radiations [v 10° Hz (1 - 380 nm)] are a component of sun's
rays and can
be produced from arc lamps containing mercury vapour, xenon or hydrogen gas, tungsten
filament lamp and hydrogen-deuterium discharge lamp.
Ultraviolet regions have two components:
Vacuum ultraviolet 1-180 nm
Ultraviolet 180-380 nm
5. Visible radiations (vs 4 x 10'* -8 x 10'* Hz (380 nm to 760 nm) are a component of the
sun's raysand are also produced from arc lamps, hot filaments of tungsten etc.
6. IR radiations (v 10" Hz) are emitted by incandescent objects. The other sources are Globar
source (silicon carbide rod when heated emit IR), Nernst Glower (composed of Zirconia.
Yttria etc.), mercury arc lamps.
The infrared regions are further divided into three sub-regions:
Near Infrared 0.7-2.5 p
Infrared 2.5-15 u
Far infrared
15-200 !
Allthree regions of electromagnetic spectrum are associated with the changes in the
of molecules. vibratiO
7. Microwaves (v 10" Hz (0.1nm to 1
cm)) are produced by special generators suu
Klystron tube. Microwave region corresponds to changes in the rotation of molecules.
Radiowaves (v 10* Hz (10 mm-1 cm) are electric currents
generated from alternating
of high frequencies. The energy change involved in this region arises due to the reversallof
spin of nucleus or electron.
 Sdeckon Rale
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Yn Co mo cles ,the euen's tmrelrel ae
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We have to take nto account
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 2 - Potntial
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(w) he elech'on le ur ibrahomal Ranan Spe ctsa
 2.3.1 Microwave Spectroscopy
The spectroscopyin the microwave regionis concerned with the study of
components about three mutually perpendicular directions through the centre of
rotating molecules
The rotation of a three-dimensional body is very complex and can be resolved into ro,
intogravity
rotationa
of gravitythe
principal axes of rotation. Thus a body has three principal moments of inertia, one abou
axis usually designated I, I and ç.
Molecules may be classified into groups according to the relative values of their the
principal moments of inertia, which in turn is relatedto their shapes.
1. Linear molecules. These are molecules in which all
the atoms are arranged in a straight line
such as hydrogen chloride HCI.
H CI
The three directions of rotation may be taken as (a) about
the bond
rotation at right angles in the plane of the paper. It is self-evident that theaxis, (b) end-over-end
(c) are the same (that is IR=I) while that of (a) is very moments of (b) and
small. As an approximation we may
say that I,= 0,
Thus, for linear molecules we have:

I, = lç and I, = 0
2. Symmetric tops. Consider a molecule suchas methyl
are bonded tetrahedrally to the carbon. fluoride, where the three hydrogen atoms
HH
H F
H
Symmetric tops: I =l#l, and I,0
3. Spherical tops: When a molecule has all
three
spherical top. A simple example is the tetrahedral moments of inertia identical, it is calleu
molecule methane CH,.
 Spectroscopic Techniques and Applications 153
H

H H
H

Spherical tops:
4.45ymmetrictops: These molecules. to whichthe majority of substances belong, have all three
different :
homents of inertia

Simple examples are water H,0 and vinylchloride CH,CHCI.

Mechanism of Absorption in Microwave and Infrared Region

The microwave region: Amolecule such as hydrogen chloride, HCI, have a permanent electric
dipole moment. H, or Cl,, on the other hand, have a zero dipole. For a pure rotation in case
of HCI molecule, the centre of gravity of the molecule remains fixed, only the plus and minus
charges change places periodically. and the component dipole moment in a given direction (say
upwards in the plane of the paper) ffuctuates regularly (Fig. 2.5). This fluctuation is exactly
similar in form tothe fluctuating electric field of radiation. Thus interaction can occur, energy
can be absorbed or emitted, and the rotation gives rise to a spectrum. All molecules having a
permanent moment are said to be 'microwave active'. If there is no dipole, as in H, or Cl,, no
interaction can take place and the molecule is 'microwave inactive'.This imposes a limitation
on the applicability of microwave spectroscopy.

Direction of)
rotation

Direction of
dipole

Vertical
component
of Time
dipole

Fig. 2.5 The rotation of apolar diatomic molecule, showing the fluctuation
in the dipole moment in a particular direction
 154 Chemistry
rotation, which nust give
infrared region: Here it is a vibration, rather than a
The carbon dioNide molecule as an example, in which the
dipole change. Consider the
with asmall net positive charge on the carbon andsmall
negativehree atomy
are aranged
on the orygens.
linearly

During the mode of vibration knovn as

'symmetric stretch', the molecule is ch argex
stretchedand compressed, both C Obonds
remains zero throughout the motion,
changing simultaneously,, as in Fig. 2.6.
and this particular vibration is thus aThel ernaditenlyol
moment
inactive'
()
Stretehed
inla-tcd
Normal

-( Compressed

carbon dioxide molecule

Fig. 2.6 The synmmetric stretching vibration of the
However., there is another stretching vibration called the anti-symmetrical stretch, deniet.
in Fig. 2.7. Here one bond stretches while the other is compressed, and vice versa. There i
periodicalteration in the dipole moment, and the vibration is thus 'infrared active'. One furth
vibration is allowed to this molecule known as the bending mode (Fig. 2.8). This is also inta.
however remains fixed
red active. The centre of gravity in any of these modes of vibrations

()

Asymmetric C
stretching C28+ C
vibration

Dipole
moment

Component
of
dipole

Fig. 2.7 The asymetric

stretching vibration of the carbon dioxide molecule,
showing the fluctuation in the dipole
 Spectroscopic Techniques and Applications 155
8 264 8
Bending O-C-0
vibration
284 8 26+

Dipole
I1ONnt

Vertical
component
of
dipole

Fia. 2.8 The bending motionof the carbon dioxide molecule and its associated dipole flue
ole chonge reauirementsdo imnose some limitation on the annlicatio1 cfir
 Infrared spectroscopy

Introduction

Infrared spectroscopy or vibrational spectroscopy is concerned with the study of absorption of

infrared radiation, which results in vibrational transitions.

Infrared radiation refers broadly to that part of electromagnetic spectrum between visible and
microwave region

Principle

When the frequency of the IR radiation is equal to the natural frequency of vibration, the
molecule absorb IR radiation and a peak is absorbed.

Every bond or portion of a molecule or functional group requires different frequency for
rotation absorption.

Theory

 IR radiations does not have enough energy to induce electronic transitions as seen with
UV.
 For a molecule to absorb IR, it must be accompanied by a change in dipole moment.
 Regions of wavelength range
Very near IR: overtone region (2-2.5µ)
Near IR: Vibration region(2.5-25 µ)
Far IR : Rotational region(25-400 µ)

Types of Vibrations
There are different types of vibrations:

Stretching (i) Symmetric

(ii) Asymmetric
Bending
(I) In-plane bending
Scissoring
Rocking
(ii) Out-of-plane bending
Wagging
Twisting
 Symmetric Stretch Asymmetric Stretch

Scissoring Rocking

Twisting Wagging

Examples

Diagram of Stretching and Bending Modes for H2O.

Solution

H2O molecule is a non-linear molecule due to the uneven distribution of the electron density.
O2 is more electronegative than H2 and carries a negative charge, while H has a partial positive
charge. The total degrees of freedom for H2O will be 3(3)-6 = 9-6 = 3 degrees of freedom which
correspond to the following stretching and bending vibrations. The vibrational modes are
illustrated below:

Figure: The vibrational modes of H2O

Diagram of Stretching and Bending Modes for CO2.

Solution

CO2 is a linear molecule and thus has the formula (3N-5). It has 4 modes of vibration (3(3)-5).
CO2 has 2 stretching modes, symmetric and asymmetric. The CO2 symmetric stretch is not IR
active because there is no change in dipole moment because the net dipole moments are in
opposite directions and as a result, they cancel each other. In the asymmetric stretch, O atom
moves away from the C atom and generates a net change in dipole moments and hence
absorbs IR radiation at 2350 cm-1. The other IR absorption occurs at 666 cm -1. CO2 has a total of
four of stretching and bending modes but only two are seen. Two of its bands are degenerate
and one of the vibration modes is symmetric hence it does not cause a dipole moment change
because the polar directions cancel each other. The vibrational modes are illustrated below:

Figure: The vibrational modes of CO2

 Factors influencing vibrational frequency:

The calculated value of wave number or frequency of absorption for a particular bond was
never found exactly same as experimental value. The reason is that vibration of each group is
influenced by the structure of the molecule in the immediate neighbourhood of the bond.
There are many other factors which are responsible for vibration shifts and one factor can not
be totally isolated from another. Frequency shifts also occur for the same substance in different
states (solids, liquids or vapours). Some of the factors responsible for shifting of vibrational
frequencies from their normal values are:

1) Couple vibration and Fermi resonance.

2) Electronic effects (inductive effect, mesomeric effect and field effect etc.)
3) Hydrogen bonding.

Isotopic Effect

Molecules having different isotopes of the same elements, such as DCl and HCl, show different
spectra. The masses of atoms are different and hence reduced mass as also the frequencies of
vibration and rotation would be different.
2.4.4.2 Sampling Techniques in IR Spectroscopy
employed for placing asample in the path of the IR beam depending o
Various techniques
gases).
the state of the substance* (solids, liquids or
1. Solids: The solid sample is dried (as water absorbs IR radiation) and grounded with alkal,
KBr etc.) which are transparent in the IR region (2.5 u-15 u) and
spectrahalides
metal (NaCl,
is taken. The spectrum ofsolids can be conveniently determined as a mull or apaste.
The mulling reagents can be (i) nujol(mixture of liquid paraffinic hydrocarbons with high
Chlorfluoro carbon oil etc.
molecular weights)(i) Hexachlorobutadiene (ii)
2. Liquids: For liquid sample,theliquid is squeezed inatthin film betweentwo sodium chlorid
plates are made wi
plates (NaClis transparent to IR). For a sample containing water, the
CaF:
chloride,
3. Gases: Thegaseous sample is introduced into a gas cell made of sodium
4. Solutions: For IR spectrum of solutions, solvents like (i)chloroform (ii) carbon tetrachloride
or (ii) carbon disulfide are used.Water can never be used as solvent as it absorbs in several
regions of IR spectrum.
2.4.4.3 Instrumentation

A
schematic diagram of an infrared spectrometer is shown in Fig. 2.24.
Sample
Wavelength
selector
Sample
holder
Source

Recorder

Director

Fig. 2.24 Schematic diagram of an infrared spectrometer

1. Source of infrared radiations: Acommon source for IR
ie arod of asintered mixture of the oxides of zircOnium, radiations
is the Nernst glower
ytterium and erbium The rod
is electrically heated to about 1500°C to produce infrared radiations. More
can be used is a silicon carbide glower. intense SourceS

For a substance to be infrared active it should either have permanent dipole moment in the molecule.
Therefore, vibrations should not be centrosymnetric.
 Spectroscopic Techniques and Applications 173
2. Sample holder: The sample holders are
materials like KBr, CaF,, usually
CsBr, AgBr, etc. are made of rock salt (NaCI) but occasionally
In modernspectrometers, NaCl prisms have also used.
been replaced by diffraction grat1ng
give better resolution at wnicn
higher temperature.
3 Wavelength selector: The source emits radiations of wide
selector permits only a particular wavelength of frequency range. Awavelengn
A radiation
Detector: Avariety of detectors are in use. Detector
between the light beams from reference and the responds to the difference in intensity
5 sample cells.
Recorder: An infrared spectrum is usually recorded as a plot of the
of each wavelength transmitted through the percentage of radiation
sample.
infrared spectrum on the chart with the help of a pen. Recorder automatically records the
2.4.4.4 Fingerprint Region
The beauty of an IR spectrum is that two identical
compounds
spectra under similar conditions of the experiment. The region belowproduce exactly the same
1500 cm' is rich in many
absorptions due to bending as well as stretching vibrations of C-C, C0and CN bonds
etc. In a spectrum, usually, there are more bending vibrations compared to stretching
The region below 1500 cm (1500 cm to 600 cm)is therefore rich in vibrations.
absorption bands and
shoulders. This region is called fingerprint region. Fingerprint region is unique for a molecule.
Some molecules having same functional groups show similar absorption above 1500 cm
but their spectra differ in the fingerprint region which indicates that main structural unit is of
different type.
An unknown compound can be identified by comparing its IR spectrum with aset of spectra
of known compounds under identical conditions. Fingerprint region can be subdivided into
three subregions:
1. 1500-1350 cml
2. 1350-1000 cm
3. Below 1000 cm!
Inthe region of 1350-1000 cm, allclasses of compounds such as alcohols, esters, lactones
show characteristic absorptions (strong bands) in this region due to C-Ostretching.
(%)
Transmittance
100

Functional group region

Fingerprint region

3000 2000 1400 I000 800 600

4000
Wave number (em)
Fig. 2.25 Functionalgroup and fingerprint region
174 Chemistry-l

2.4.4.5 Applications of IR Spectroscopy

The IR spectrum is ahighly characteristic property of asubstance and provides more
than available from electronic spectra. The IR spectroscopy helps us to know the
foilnfoowirmnag:ti n
1. Detection of functional groups: The IR spectroscopy 1s
commonly-employed for
identification of characteristic functional groups such as (C=0)-OH,-C= N, etc.
in the given compound. present
2. Identiñcation of a Compound: The compound itself may be identified by the
region(below 1500cm) of the spectra. No two compounds have the same
fingerpr1fi
ntnger
if the conditions for scanning spectra are kept fixed. In case of two homologues differa,
pri
spectn
in CH, group viz., CH,OH and CH,CH,OH, the spectra will differ in the
region. One can predict whether the compound is aliphatic or aromatic. One can
what kind of isomers are present.
fin ger prin
identitt
3. Detection of impurity: The presence of impurity in a compound may be detected from
thenature of IR bands which no longer remain sharp and well-defined. Hence, IR spectrum
of a compound serves as a criterion of purity of a compound. Qualitatively, as well as
quantitatively the amounts of various substances present in the mixture can be determined
from their IR spectra.
4 Presence of hydrogen bonding: Due to hydrogen bonding in acompound, the given peak
is shifted to lower frequency.
5. Presence of conjugative groups: Conjugation lowers the absorption frequency. Hence,
presence of a conjugative group can be ascertained from the study of IR spectra.
6. Studying the progress of reaction: IR spectral studies can be used to follow the progress
of a reaction. During the course of a reaction, many intermediates get formed which then
change into the products These intermediate compounds can be identified by IR spectroscopy.
IR spectrometer records the spectra continuously and the reaction can be followed by
interpreting the spectra and the mechanism of the reaction can be proposed.
The characteristic IR absorption regions of some important bonds are given in
Table 2.1.
Table 2.1 Some characteristic infrared absorption regions
Bond Type of compound Wavelength (in um) Frequency (in cm)
H
Alkanes 3.38-3.51 2850-2960
-CH
Alkenes 3.22-3.32 3010-3100
C-H
Alkynes 3.03 3300
C-H
Aromatic rings 3.22-3.33 3000-3 100

H Aldehydes 3.47-3.77 2650-2880

C--H Aromatic rings 6.25-6.66 1500-1600

Alcohols, ethers,
-R carboxylic acids, esters 7.7-10 1000-1300
 Spectroscopic Techniques and Applications 175
Bond
Type of compound Wavelength (in um) Frequency (n cm')
0H Monomeric alcohols 3600-3650
and phenols 2.74-2.78

-0-H
Hydrogen bonded 2.94-3.11 3200-3400
alcohols and phenols
Hydrogen bonded acids 3.33-4 2500-3000

Amines 2.86-3.03 3300-3500

244.6 IR Spectrum of Some Organic Compounds

1. Infrared spectrum of aliphatic hydrocarbon (3-methyl pentane)
Wavelength in microns
2.5 3 4 5 6 7 8 10 11 12 13 14 15
100
Percentage
transmittance
80

60

40

20
A B C D

4000 3000 1500 1000 667

Wave number in cm-!

Fig. 2.26 Infrared spectrum of 3-methyl pentane

C-Hdeformation
It has characteristic absorptions with C--H stretching at 2940 cm,
bands at 1450cm- and at 1370 cm.
hydrocarbon (benzene)
L. Infrared spectrum of aromatic
Wavelength in microns
6 12 14 15
2.5 3 4
Percentage
transmittance
100

80

60

40

20

2000 I800 1600 1400 1200 1000 800 667

4000 3500 3000 2500
Wave number in cm-!
benzene
Fig. 2.27 Infrared Spectrum of

stretching bands at 3050-3000cm",C-Cstretching in the region

nas characteristic Ar H
of and C-H deformation band at 900-700 cm.
1600-1450 cm
176 Chemistry-I
(CHCH,CHCOCH,):
3. Infrared spectrum of 2-pentanone Wavelength in microns
6 10 12 14 15
2.5 3 4
Percentage
transmittance
100

80

60

40

20

4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 667
-1
Wave number in cm

Fig. 2.28 IRspectrum of 2-pentanone

It has characteristic band forCO group at 1700 cm'. The CH stretch is at about 3000 cm !
and CH, band at around 1400 cml

2.4.5 Rotation-vibrationSpectra due to Electronic Transition

The electronic spectra are studied both in emission and absorption. When an electron of a
molecule is promoted from a low energy state to a higher energy state, radiations are ab_orbed
in discrete amounts giving rise to absorption bands. On the other hand during the return of an
excited molecule to lower electronic states, energy released leads to emission spectra. Relatively
large amounts of energy changes (about 10 kcal/mole) are involved in these and the spectra are
found in the visible or ultraviolet region.
Any change in the electronic state is associated with simultaneous changes in vibrational
and rotational levels. When an electronic state is altered, there are usually a large number ot
changes in vibrational levels, each of which gives rise to a band. In each of these bands again
thereare innumerable lines due to rotational transitions.
This makes the electronic spectra, even of very simple molecules, quite complicated.
Now, the energy of the molecule
E -E,, + Eih t Epol
In two electronic states, we can express them, as

..(2.31)
E=Eel hxo+ BhJ(J + 1)

and ..(2.32)
E'El hx'¡ + B'hJ'J'+ 1)
where and are the vibrational quantum levels in two states with different fundament
u asalso
frequencies o and o'; the rotational constants B and B' different
anharmonic factors x and x'. Subtracting, consequently will be
AE= hv, t
hxo-(v+]ho
+BhJJ + 1) B'hJ'(J' + 1)
-.(2337
 beSeV therefore
nence, given perchange A The Ultraviolet UV
Oniar UVFar,
oy molecule.
by UV ultraviolet
Near
radiation
rULTRAVI
adiatstioanrtOs LET
ultraviolet the hy in or region
Oxygenspectrum
= is
electronic
5 involved vacuum,
and xThe is at
has subdivided the
region in 1.6
nitrogen frequency sufficient AND
the x state withultraviolet blue
C 10-1
5x1.6x
10l2V. =
(belowvisible electronic VISIBLE
end
ergs is into
and associated (v) energy of
Cxh two the
it190 and of 190-380nm
requires nm) UV excitation.
the SPECTROSCOPY
1-190
to nm spectralvisible

region lines with excite

is light
vacuum not x6.6x10-27
3x10" produced avalence regions.
is larger (about
much
5x1.6x10-12
the
struments.electronic differenceelectrons 380
studied due
to nm)
due electronic and
spectrum. 250nm
= energy
in atoms of
to ends
absorption transition or at
molecules
of about
the
order 190
of would nm.
such and
of
178 Chemistry-I

2.5,1 Laws of Absorption

laws which govern the absorption of light by themolecules. These are:
There are two
1. Lambert's Law
2. Beer'sLaw.
radiation passing through a
1. Lambert's
transparent, ILaw: For
absorbing
directly
medium,
proportional tothe
monochromatic
of rate
a beamthe
homogeneO
of decrease of intensity of radiation with thickness o
intensity of the incident radiation.
medium is
Mathematically, this can be represented as
dl
dx .234
di
= KI
dx
the medium and:
where I is the intensity of radiation after passing through a thickness x, of
the infinitesimally small change in the intensity ofradiation on passing through the infinitesimal.
small thickness,dx of the medium.
The-ve sign implies the decrease in intensity.
K is the proportionality constant or absorption coefficient whose value depends upon the
nature of the absorbing medium.
Let, I, be the initial intensity of radiation, i.e., radiation before entering the absorbing medun
(r=0).
Then I,the intensity of radiation after passing through the thickness 'x' of the medium can te
calculated by integration. The boundary conditions are () I =I, when x=0 and (i) I=l, whe
x=x, i.e., I is the transmitted intensity of the radiation.
dl x=X

=-kx, or I=Ie
The intensity of radiation absorbed, Iohe is given by
Labs =o-I= I,(1 - e)
By changing the natural logarithm to base 10, we have
I1,10
where a is the extinction coefficient of absorbing medium
k
a
2.303
2. Beer's Law: For a beam of bomogeneous
monochromatic
transparent solution of an absorbing radiation
substance, the rate ofpassing through
decrease in the aintensity ofthe
radiation with thickness of the absorbing solution is directly proportional to the Concentratiol
of the solution.
Mathematically, this can be represented as
di
dx
 Spectroscopic Techniques and Applications 179
Now, combining Eqs. (2.38) and
(2.39), we get
d
dx
d
Or d al·C
d
or
=ay Cd
...(2.40)
where a,y 1S the proportionality constant. The quantity Cd
ner unit area of the layer, dx is the measures the amount of substance
thickness of each successive layer.
Since C=
Mole Mole
Volume Area x Thickness
Hence, Cax = Mole Mole
Area x Thickness x Thickness Area
Now integrating equation (3) with the boundary conditions (i) I= I, when x =0and
(i)I=1, when x=x, we have
dl
=-oyC£t
or In a,Cx
where a,,is the absorption coefficient and is a function of frequency or wavelength of incident
radiation. In the logarithm scale

-Cx
log 2.303

Of loge =e,C* or I= 1,10-e,C ...(2.41)

Oy and is called the 'molar extinction coefficient' and is a function of frequency

where & 2.303
or wavelength. The concentration C" is expressed in moles per litre and 'x' is the optical path
length in 'cm'.
In SI units C, x and e are mole dm, metre (m) and n mol respectively.

I, and I are the incident and transmitted intensities respectively. The quantity log - e is
commonly known as optical density OD or absorbance A.
The amount of light absorbed he by the media is given by
,-I=I,-1,10y =L,(1-10E,C) ...2.42)
Lohe
For more than one absorbing species in the media, the optical density is , Cx, where
 180 Chemistry-I

Jo

Light source Lens Filter

Slit Cuvette

absorption measurement
Fig. 2.29 Optical arrangement for
whose
E, is the molar absorptivity at frequency v,
for the ith component concentration is c
The measured OD is then

OD = 0D, + OD, + OD, +...OD, ..243

Now, A= ,Cx
where C=1 mole dm3 and x=lcm
A= E, or FA
Thus, molar absorption coefficient or molar extinction coefficient is the specific absorio
coefñcient for a concentration of 1mole dm and a path length of 1cm.
Different molecules absorb radiation of different wavelengths. An absorption spectrum wil
show a number of absorption bands corresponding to structured groups within the molecuke
From this, the structure of molecules can be assessed.

2.6/ELECTRONIC TRANSITIONS
Energy absorbed in the UV region produces changes in the electronic energy of the molecuk
resulting from transitions of valence electrons in the molecule. The types of electrons involved
in organic molecules are:
1. g-electrons: These electrons are involved in saturated bonds, such as those between cartu
and hydrogen in paraffins. These bonds are known as o-bonds. The o-bond energy is higher tä
that produced by UV light and hence G-bonds do not absorb UV radiation.
2. TT-electrons: These electrons are involved in unsaturated
hydrocarbons like trienes a
aromatic compounds.
3. n-electrons: These electrons are not involved in any bonding. Organic compounds
nitrogen, Oxygen or halogens are the examples.
The other types of electrons involved are charge transfer
are common in inorganic complexes.
electrons and dand felectrons W
According tomolecular orbital theory, when a molecule
(UV or visible radiation), its electrons are promoted from isa excited
bonding by
tothe
an absorption
antibondingof orbial
e
When oelectron is s excited to antibonding o orbital (o*)it is represented as o ’o* transitio
When -electron is excited to antibonding -orbital (r*), it is represented as ’ T* transition
 Spectroscopic Techniques and Applications 181
Similarly., when a non-bonding electron (n) gets promoted to
antibonding T-orbital (*), antibonding o orbital (o )
representations will be n ’ o* and n ’ n* respectively.

g*
Antibonding
Energy
T
Antibonding
n Nonbonding
n’ *
Bonding

o’ * Bonding
Fig. 2.30 Electronic excitation energies Fig. 2.31 Various electronic energy levels
The energy required for various transitions follow the order
g ’ o* > n-g* > -T* > n ’ *
The main features of o’ o*, n’ o*, n ’n* and ’ n* transitions are:
1. G’ o* transitions: The bonds are very strong. The energy required for such atransition
is very large and thus requires radiations of high energy (short wavelength). The absorption band
of such transitions occurs in the far ultraviolet region (120-135 nm). For example, transitions of
methane and ethane occur at 122 and 135 nm respectively. The commercial spectrophotometers
cannot be used below 200nm as oxygen and nitrogen absorb strongly. In order to do so the entire
path length should be evacuated to remnove air. The region below 200 nm is therefore commonly
called 'vacuum ultraviolet' region.
g ’ g*

2. n ’ g* transitions: This type of transition takes place in saturated compounds having

hetero atom with unshared pair or non-bonding electrons (n electrons). The energy required for an
n’ g* transition is less and the corresponding absorption bands appear at a longer wavelength
in the near ultraviolet (190 - 380 nm) region.
Some comnpounds undergoing this type oftransitions are saturated alcohols, ethers, aldehydes,
ketones, amines, alkyl halides etc.
Compounds Absorption maxima
Methyl chloride 170 nm
Water |67 nm
Methyl alcohol 175 nm

Trimethyl aminc 227 nm

well as amines are
n’ o* transitions are very sensitive to hydrogen bonding. Alcohols as
Known toform bydrogen bonding with solvent molecules. The bonding is due to the presence of
hon-bonding electrons in the hetero atom and thus transitionrequires greater energy. Hydrogen
Donding therefore shifts the UV absorptionto shorter wavelength (high energy).
 182 Chemistry-I
n’ *

3. n’ T* transitions: This type oftransition occurs in unsaturated compounds

(comne.
with double or triple bonds) including aromatics. The energy required for such atransition is
small andtherefore occurs at alonger wavelength. The absorption peaks for these transitions fall
in the experimentally convenient region of the
spectrum (190 to 380 nm). The molar
coefficient of n ’ * transitions are between 1000 to
10,000 litres mol cm Inextinction
compounds the I ’ * transition appears at 180 nm and in
unconjugated alkenes at
linkage produces a
cararound
bathochromi
bonyl
-d
170-190 nm. The introduction of alkyl group to olefinic
(red shift, i.e., towards longer wavelength) of theorder of 3 to 5 nm per alkyl group. The sk:a
depends on the nature of alkyl group as well as on the stereochemistry about the double bond.
For some substituted olefins, trans isomer absorbs at longer wavelength with greater intensity
than the cis isomer. With increase in the length of conjugation the difference between trans and
Cis isomers increases.

4. n’ * transition: These types of transitions are shown by unsaturated molecules which

contain a hetero atom such as oxygen, nitrogen and sulphur with unshared pair of electrons.
This type of transition requires small amount of energy and thus occurs at longer wavelengths.
R
Saturated aldehydes show both low energy n ’ T* and high energy T’ n*
H
transitions around 290 nm and 180 nm respectively. The extinction coefficient at lower wavelength
isquite high compared to that at a higher wavelength. Thus, by measuring extinction coeficient
the type of transition can be predicted. Incarbonyl compounds, a high energy n ’ o* transition
also occurs, and is quite intense. Thus, in saturated carbonyl compounds, two types of transitions
take place
(a) High energy transitions:
() n’o* (intense) (ii) n ’ * (intense)
(b) Low energy transitions n’ 1* (weak)
In carbonyl compounds, the shift in absorption band is found to depend on polarity of thR
solvent.

2.6.1 Absorption of Radiation and Transition Probability

When frequency of incident radiation (v) is equal to the frequency of oscillation of themolecule.
atot
the molecule (v.) a resonance condition is established between the photon and the
Under such conditions a quantum of radiationor aphoton is absorbed.
Thus, for a compound exposed to radiations it is not essential that it willabsorb light
transition probability is found to depend on the value of molar extinction coefficient as wel
its symmetry. Transitions can therefore be divided into two categories:
1. Allowed transitions
2. Forbidden transitions
 183
Speclroscopic Techniques andIApplications

I,
Allowed(ransitlons: Gencrally, the transitions for which molar extinction coefficient
to be 10" or more are called allowed transitions. These generally arise for n’
transitions, For example, in I,3 butadiencthe about
n21000andare thereforc ocalled allowcd transitions.absorption maxima at 217 nm have max
Forbldden transitions: For transitions with molar extinction coefficient (Emaxd that are
2.
than104 are called forbidden transitions. These generally arise for n
less * transitions. For
example, saturated aldehydes or ketones with absorption maxima at around 300 nm have max
thatarelcss than 100 and arc callcd forbidden transitions.
As tàr as symmetry restrictions are concerncd, a totally symmetrical molecule has more
restrictionsthaan a totaly unsymmetrical molecule. For example, benzene has more restrictions
transition and hence the spcctrum is simple. For an unsymmetrical molecule the electronic
onits
spectrum willbe complex.
In general, transitiondepends on the geometry of ground as well as excited state moecular
orbital and also on the orientationof the molecule with respect to electric field of the radiation.

(a) Chromophore
Agroup which shows acharacteristic absorption in the ultraviolet or visible region of the
spectrumm is calledchromophore.
Itmay or may not impart any colour to the compound. For example, in nitro compounds the
nitro group imparts colour to the compounds and it appcars yellow. On the other hand, a carbonyl
group in isolated condition does not give rise to any colour in UV spectroscopy.
The examples of some important chromophore groups are ethylenic, acetylenic, carbonyls,
acids, nitriles etc. Chromophores are of two types:
(a) Chromophores in which the group contains r electrons which undergo n’ * transitions.
Examples: Ethylenic and acetylenic groups etc.
(b) Chromophores having both T-electrons and n(non-bonding) electrons which undergo two
types of transitions, i.e., n’ n* and n ’ *.
Examples: Carbonyls, nitriles,nitro compounds and azo compounds etc.
(b) Auxochrome
Anauxochrome is a group which does not itself act as a chromophore but when
attached to a
chromophore it shifts the absorption maximum towards the longer wavelength alongwith an
Increase in the intensity of absorption. An auxochrome group is therefore known as colour
enhancing group.
AUxochrome groupsdo not show characteristic absorption bands above 200 nm. Auxochromes
dctually have one or more non-bonding pair of electrons and when attached to a chromophore,
neips to extend conjugation by sharing of non-bonding electrons causing bathochromic effect
(Shifting of absorption band towards the red end).
CH,-CH-NR, + ’ :CH,-CH=NR,
Ihe addition of auxochrome to a chromophore results into a new chromophore. The new
Sromophore results in anew absorption maximum as wellas extinction coefficient. Thus, when in
alauxochrome-NH, group is atached to a benzene ring, its absorption changes from 2Mmay 255 nm
(Ema, 205) to Mmax 280 nm (Em 1430).
184 Chemistry-I

OH, -OR, NH,, - NHR,

The most common auxochromic groups are
SH etc. NR, and
2.6.2 Position and Intensity Shifts of Absorption
1. Bathochromic effect: The shift of absorption maxima towards longer wavelength bera
of the presence of an auxochrome or by change of solvent is known as red shift or
shift. For example, the decrease in the polarity of solvent causes a redshift in the n
absorption of carbonyl compounds.
bathochro’*miç
Bathochromic effect is also observed for compounds containing chromophores which
in conjugation. Thus, whereas ethylene shows 1-* transition at 170nm, 1,3-butadiene
absorption maximum at 217 nm. shows
2. Hypsochromic effect: In this case the shift ofabsorption maximumoccurs towards shotes
wavelength (Blue shift).
Such an effect may occur due to the removal of conjugation or by change in solvent polari

For exåmple, in case of aniline

NH,
absorption maximum occurs at 280nm due
tothe pair of electrons of nitrogen atom which is in
conjugation with the t bond system of the
benzene ring. Inacidic solution, a blue shift is caused and
absorption occurs at shorter wavelength
(-200 nm) due to formation of NH,
where conjugation is non-existent.
3. Hyperchromic effect: It is an effect due to which there is an
absorption usually brought about by the introduction of an increase in the intensity of
of methyl group in position 2of
pyridine auxochrome. For example, introduction
2750to 3560 (2."max 262 nm) for ’ n*
(2-methyl pyridine) increases .m (mmax 262 nm) from
transitions.
4. Hypochromic shift: It
coefficient .o decreases. involves
a decrease in the
intensity of absorption, i.e., the extinction
The introduction of the group
molecule causes hypochromic effect. Thus, when a which distorts the geometry of the
the biphenyl group, the max methyl
to distortion caused (max 250 nm) 19000 changes togroup isintroduced in
position 20t
Emax (may 237 nm) of 10250 due
by methyl groups.
2.6.3 Effects of
Conjugation
Theenergy for transition is
bonds in conjugation, lowered with conjugation of double
may become absorption may ultimately occur in the bonds. If there are enough dou
in coloured. In caseof conjugated polyene visible region and the compou
conjugation the absorption 0ccurs in the visible regionsystem
of alkyl group on the with more than five double bonds
shift in absorption anddouble bond also causes red shift.Foraround or above 400 nm. The presei
shift is 30 nm. The for each double bond each alkyl
double bond. molar absorptivity (e,mn) extending conjugation substitution
in
there IS
In case of
aromatic
also roughly
doubles T-electron systel
with each new conjugated
180 nm (Cmax
~62,000),compound such as
weak absorption at benzene the
200 nm strong absorption band is obtainedweaker
near
(Em7,500) and
a group of much
 Spectroscopic Techniques and Applications 185
the region between 250 nm to 300 nm (.200). In the absorption maximum for
bandsin
conjugation.as in naphthalene, anthracene, tetracene and pentacene, the absorption moves
added
tolonger waavelength, i.e., the absorption shifts from UV region to visible region.
R(CH= CH),R

n=5

Energy
n=4
ENTR. ¡RMATION
PODOAR
n=3 BANK

200 300 380

(nm)
Fig. 2.32 UV-visible absorption spectra of linear conjugated polyene
added conjugations.
The molar extinction coefficient is also found to increase with

5.0

log [ 4.0

3.0

2.0
400 S00
200 300
A(nm)
of aromatic linear condensed systems
Fig. 2.33 UV-visible spectra
Transfer Complexes (Charge-transfer Band)
2.6.4 Electronic Transitions for Charge together,
molecules, which may not be coloured, when mixed
Ihere are instances in which two visible region. The colour shifting is due to
generally in the
new absorption band produce charge transler complex between the pair of molecules.
TOmation of complexes known as transition molecule with high
of an electron from the (electron-deficient).
Fomation of the complex is due to the
molecule with low charge density
Cnarge density (electron-rich) to the
rved:
shiftsare changing the
arbonyl shiftabsorption, etc., Therefore, 210 under Solvent 2.6.5
ForEffects
The SolventsSolvents
remains nm
areUV-spectroscopic
position
pounds used investigation as
in which well
almost
polarity such solvents
the but
and as
range asnon-polar are
are
unaffected
the intensity of benzene, less such and
transparent
of
study,
polarity the
240-280preferred asless is
solvent.
ofabsorption are
hexane, the
with chloroform solvent
of used polar
above
solventchange In nm,compared
cyclohexane, for so
case are 210 is
maximum UV-spectroscopy. that so
has in of not and to nm chosen
the
great
polarity.dienes used.carbon other but interaction
are diethyl that
effect. shifted and is nonpolarpolar, it
However, tetrachloride does
conjugated ether with
In for solvents. such not
such
in a as whichsoluteabsorb
particular
pounds case
hydrocarbons, because water,
molecule
radiations
are
of ethanol,
chromophore transparent
a, of
two B
unsaturated their 1s in
types the methano.! minimum. the
band strong above region
of by
 Spectroscopic Techniques and Applications 187
1 M->I* transition (less intense): In this case, with increase in
polarity of solvent the
ksarmtion band shittstoshorter wavelength. Inn -> *transition, the ground state is more polar
naredto excited state and hence the solvent molecule stabilizes the non-bonding electron
in the ground state due to hydrogen bonding. In the excited state, the hydrogen bond1ng with
cartonylgroup takes place to lesser extent compared to the ground state. Thus, incase of acetone
the absorption maximum isat 280 nm in hexane as compared to 264nm in water.
2. n’1* transition (intense): In this case, the absorption band moves to longer wavelength
with increased polarity of the solvent. The dipole-dipole interactions with solvent molecules
lower the energy of the excited state compared to the ground state. Here, the group is more
polar in the excited state and thus the * orbital in the excited state gets stabilized by hvdrogen
bonding with solvents such as water, methanol, ethanol, etc., and absorption shows a red shift.
n ’ o* transitions are also very sensitive to hydrogen bonding. For example. alcohols,
amines etc.,form hydrogen bonding with solvent molecules due tothe presence of non-bonding
electrons in the hetero atom( 0 , = N )and thus transitions require greater energy and a
blue shift results.
Z.6.6 Applications of UV Spectroscopy
G nain applications of UV spectroscopy are: (1) Qualitative and quantitative analyses of
pounds. (2)Detection ofimpurities in organic compounds. (3) Determination of molecular
weights. (4) Determination of dissociation constants of acids and bases.
 efc.
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