B.

Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)

MODULE -2 Spectroscopic Techniques and Applications

[Elementary idea and simple applications of Rotational, Vibrational, Ultravoilet & Visible and Raman
spectroscopy]
SPECTROSCOPY

Spectroscopy is the analysis of the electromagnetic radiations scattered or absorbed or emitted by

molecules. It is study of interaction between electromagnetic radiation with the matter and is a most
powerful technique to study the atomic and molecular structure of the compound.

Significance of Spectroscopy:
• Less time consuming.
• Very small amount of sample required.
• Substance remains unchanged during spectroscopic examination and can be used again for other
tests.
• Cost effective

Electromagnetic radiation consist of discrete packages of energy which are called as photons.
A photon consists of an oscillating electric field
(E) & an oscillating magnetic field (M) which are
perpendicular to each other.
 Frequency (ν):
– It is defined as the number of
times electrical field radiation
oscillates in one second.
– The unit for frequency is Hertz
(Hz).
1 Hz = 1 cycle per second
 Wavelength (λ):
– It is the distance between two nearest parts of the wave in the same phase i.e. distance
between two nearest crest or troughs.
 Wavenumber ( ʋ ):
– It is ,the number of wave cycles per centimeter
, which is the reciprocal of wavelength and is
-1
expressed in cm .

The energy of photon given by a equation:

∆ E = h ʋ (1)
where: h = Planck’s constant , Proportionality constant
λ wavelength, λ = c/ʋ
(c = velocity of light, 3 x 1010 cm s-1 ).
When ʋ = c/ λ is substituted in eq. (1) :
∆ E = hc/ λ

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Fig.:Emission and Absorption of radiations ∆E = E2 – E1 = hc/λ = hν

Depending upon the EMR absorbed or emitted by an atom or molecule, any of the following two types of
spectrum can be used in a particular type of spectroscopy:

(i) Absorption Spectrum: It results when an atom or molecule undergoes a transition from the lower
energy level to the higher energy level with the absorption of a photon of energy hν, provided hν is exactly
equal to the energy difference ( ∆E = E2 – E1 ) between the two levels.

(ii) Emission Spectrum: It results when the atom or molecule falls from the excited state to the ground
state with the emission of a photon of energy hν.

Depending upon the type of species (atom/ molecule etc.) involved, spectra can be divided as:

(i) Atomic Spectrum: It arises from the transitions of an electron between the atomic energy levels.

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(ii) Molecular Spectrum: It arises from the transitions of an electron between the molecular energy levels.
Molecular spectrum gives more information about the structure as it not only includes electronic energy
(atomic spectrum) but also vibrational energy, rotational energy and translational energy.

Interaction of EMR with Matter

Types of molecular energy:

1. Electronic Energy Levels
2. Vibrational Energy Levels
3. Rotational Energy Levels
4. Translation Energy Levels

Total energy of molecule = Eelectronic + Evibrational + Erotational + Etranslational

( Etranslational The translational energy is very small , it is dissipated as heat and not involved in the
molecular spectroscopy.)

Total energy of the molecule:

S.No Spectroscopy Transitions Electromagnetic

spectrm
1. Rotational Between Rotational Microwave
Energy levels
2. Vibrational or IR Between Vibrational Infrared
Energy levels
3. Electronic or UV- Between Electronic Energy UV-visible
visible levels

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ULTRA VIOLET – VISIBLE (UV-VIS) SPECTROSCOPY (ELECTRONIC

SPECTROSCOPY)

Q.1 What is Absorbance Law or Beer-Lambert’s Law. Derive and write its limitations.
Ans. The Beer-Lambert ‘s Law :It states that for a parallel beam of monochromatic radiation passing
through a homogenous solution the absorbance is proportional to the product of the concentration and path
length.

A ∝ c. l
A = c. l
where:
A = absorbance
ε = absorptivity
l = pathlength
c = concentration
ε is absorptivity constant. Its value depends on the substance, solvent, wavelength and the units used for the
concentration and path-length

Derivation:
When a beam of monochromatic light is passed through a solution of an absorbing substance, the
rate of decrease of intensity of radiation (‘dI’ ) with thickness of absorbing solution (‘dl’) is directly
proportional to the intensity of incident radiation (I), as well as concentration of the solution( c).

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Mathematically, according to Beer-Lambert’s law;

On integrating Eq. (1);

When intensity is I0 (incident), the path length is zero and when intensity becomes It (transmitted), the path
length becomes l;
I = Io at l = 0
I = It at l = l
We get,
∫ ∫

By taking natural logarithms,

where,
ε = K/2.303, is called the absorption coefficient or absorptivity
log Io/ I = A, is called the absorbance

;
𝑨 𝛆𝑪𝒍

Transmittance (T): It is the ratio of the intensity of transmitted light ( I ) by the sample to the intensity of
incident light on the sample ( Io ).
T = I / Io
%T = T x 100

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Absorbance(A): It is the reciprocal of the logarithm of the transmittance.

A = -log T = - log (I / Io) = log (Io / I)
This relationship may be expressed as:

Two common methods of expressing the constant are :

(i) Absorptivity (ε): Absorptivity is the absorbance at specific wavelength when the concentration is
1gm/L and the path length is 1cm.
 = Lgm-1 cm-1
A=c.l

(ii) Molar absorptivity (εm ): Molar absorptivity is the absorbance at specific wavelength when the molar
concentration is 1mole/L and the path length is 1cm.  m = Lmole -1 cm-1

A= mcm.l [ molar concentration = conc./ mol.weight ]

Let Io is the intensity of incident and I is the intensity of transmitted light.

Limitation of Beer-Lambert’s law:

(i) The electromagnetic radiation should be monochromatic.
(ii) The light beam should not be scattered.
(iii) The solution should be diluted.
(iv) Deviation may occur, if the solution contains impurities.

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Practice Questions:

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Q.3 Explain the principle and application of UV- visible spectroscopy.

Ans. Ultraviolet- visible spectroscopy involves the absorption or emission of ultraviolet/visible light by a
molecule causing the transition of an electron from a ground electronic state to an excited electronic state
or vice –versa.
 The region of UV-visible spectroscopy : 200 nm to 800 nm .
  It depends upon the nature of electrons present.
 The common solvent used for preparing sample to be analyzed is either ethyl alcohol or
cyclohexane.

 Ultraviolet- visible spectroscopy is used to measure the number of conjugated double bonds and
also aromatic conjugation within various molecules.
 Maximum Wavelength  max : The wavelength at which absorption maximum occur. It indicates
the position of absorption band.







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Application of UV- visible spectroscopy:

(i) Detection of Conjugation:UV-visible spectroscopy is an important tool to determine the extent of

conjugation in polyenes (compounds having more than one double bond). With increase in
conjugation the max shifts towards the longer wavelength .

(ii) Detection of impurities: UV- visible absorption spectroscopy is one of the best methods for
determination of impurities in organic molecules. Additional peaks can be observed due to impurities in
the sample and it can be compared with that of standard raw material.

(iii) Quatitative analysis: Determination of molecular weight using Lambert’s Beer’s law. A=c.l
where: A = absorbance, ε = absorptivity ,l = path length ,c = concentration

(iv) Detection of geometrical isomers : Geometrical isomers can be distinguished by UV-visible

spectroscopy. The trans isomer exhibit max at slightly longer wave length than the cis-isomers.
trans –stilbene absorbs at longer wavelength ( max=295nm) (low energy)
cis –stilbene absorbs at shorter wavelength ( max=280 nm) (high energy) due to stearic effects

(v) Qualitative analysis: UV- visible absorption spectroscopy can be characterize those types of
compounds which absorb UV-visible radiation. Identification is done by comparing the absorption
spectrum with the spectra of known compounds.

(vi) Study of kinetics of chemical reaction . The UV-visible radiation is passed through the reaction
cell and the absorbance changes can be observed. As we know that absorbance is directly proportional
to concentration.

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(vii) Quantitative analysis :Used in quantitative analysis of pharmaceutical substances and drugs.

Q. 4 Describe the various types of electronic transitions.

Ans. Absorption of UV-Visible radiation by an organic molecule leads to electronic transitions between
various energy levels. These transitions consists of an excitation of an electron from an occupied molecular
orbital to unoccupied molecular orbital.

HOMO(Highest occupied molecular orbital) LUMO(Lowest unoccupied molecular orbital)

LOMO(Lowest occupied molecular orbital) HUMO(Highest unoccupied molecular orbital)

The possible electronic transitions :

I. σ → σ* transition:
• These transition occur by the saturated hydrocarbons.
• Transition occur by σ electron from bonding orbital is excited to corresponding σ* anti-bonding
orbital.
• These transition require higher energy and thus absorb radiation at lower wavelength.
• e.g. Methane , ethane propane etc.

II.n → σ* transition:
• These transition occur by the saturated compounds containing atoms with lone pair of
electrons like O, N, S and halogens .
• They are capable of n → σ* transition.
• These transitions usually requires less energy than σ → σ* transitions.
• e.g. Amine, aldehydes, alcohol , alkyl halide, ethers, etc.

III. π → π* transition :

• These transition occur by the π electron in a bonding orbital to corresponding anti-bonding orbital
π*.

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• These transition are associated with compounds containing double or triple bond and aromatic
compound.
• These transition require less energy and occur at higher wavelength.
• Compounds like alkenes, alkynes, carbonyl, nitriles, aromatic compounds, etc undergo π
π* transitions.

IV.n → π* transition :
• Unsaturated compounds containing heteroatoms such as O,N,S show this type of
transition.
• An electron from non-bonding orbital is promoted to anti-bonding π* orbital.
• Compounds containing double bond involving hetero atoms (C=O, C≡N, N=O) undergo such
transitions.
• n → π* transitions require minimum energy and show absorption at longer wavelength around
300 nm.
• Aldehydes, ketones, cyanides, carboxylic acid etc.

Electronic transitions in the order of increasing energy:

Q.5 Define the following terms: (a) Chromophore (b) Auxochrome.

Ans. (a) Chromophores :
 The part of a molecule responsible for imparting colour, are called as chromophores.
 It is covalently bonded unsaturated group responsible for electronic absorption.
 Chromophores shows absorptions due to n →π* & π → π* transitions.
 There are two types of chromophores:
(a) Chromophores containing  electrons; they undergo π → π* transition,
For e.g. ethene (–C=C-), ethylene (-CC-) etc.
(b) Chromophores containing both π and n electrons; they exhibit two types of transitions: π → π* and
n → π* e.g. >C=O, CN,

 e.g. NO 2 , N=O, C=O, C=N, C≡N, C=C etc

 When double bonds are conjugated in a compound λmax is shifted to longer wavelength.
e.g. 1,5 - hexadiene has λmax = 178 nm
2,4 - hexadiene has λmax = 227 nm

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(b) Auxochrome
 An auxochrome is colour enhancing group.
 When it is attached to chromophore, it changes intensity as well as the wavelength
of the absorption maximum.
 They are saturated groups having lone pairs of electrons .
 Auxochrome generally increases the value of absorption maxima by extending the conjugation
through resonance.
 e.g NH2 , OH, OR, NHR, –SH etc.

Note: Benzene is colorless but aniline is yellow in color due to presence of an auxochrome –NH2 in
aniline.

Q.6 Explain the intensity and absorption shift.

Or Define the following terms: (i)Bathochromic (ii) Hypsochromic (iii) Hyperchromic
(iv) Hypochromic shifts.
Ans. When an absorption in a molecule is affected either by any structural environment or by solvent, it
gets shifted. The absorption may shift by intensity or by wavelength. The various shifts are:

Fig: Absorption and Intensity Shift

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(i) Bathochromic shift (Red shift) :-

• The effect which cause shifting of absorption maximum towards longer wave-length is called
Bathochromic shift.
• Red shift may be affected by:
a. The change of medium.
b. The presence of an auxochrome.
c. The presence of conjugation.
For e.g. CH2 =CH2 ((max = 175 nm) ;
CH2 =CH-CH=CH2 ((max = 217 nm)

(ii) Hypsochromic shift (Blue shift) :-

 The effect which cause the shifting of absorption maximum towards shorter wave-length is called
Hypsochromic shift.
 Blue shift may be produced by-
a. The removal of conjugation
b. The removal of an auxochrome
c. The change in solvent polarity.

For e.g. Aniline exhibits blue shift in

acidic medium because of the removal of
conjugation of non-bonding electrons
with benzene ring in anilium ion.

(ii) Hyperchromic shift :-

 The effect which cause an increase
in the intensity of absorption
maximum (εmax ) is called
hyperchromic shift.
 It is usually effected by the
introduction of an auxochrome.

(iv)Hypochromic shift :-
• The effect which cause the
decrease in the intensity of
absorption maximum (ε max ) is called
hypochromic shift.
• It is caused by the groups
which distorts the geometry of the
molecule.

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Q.7 Explain the conjugation and solvent effect.

Ans. Conjugation effect :
 When two or more chromophores are conjugated , the absorption maxima is shifted to a larger
wavelength or shorter frequency.
 In conjugated systems, the energy separation between the ground state and excited state is reduced
and the system absorbs at longer wavelength (higher λmax ) with larger intensity (higher ε max ).
 Therefore, Longer the conjugation = Larger the λ max

 When double bonds are conjugated in a compound λmax is shifted to longer wavelength.
e.g. 1,5 - hexadiene has λmax = 178 nm
2,4 - hexadiene has λmax = 227 nm

Solvent effect:
• The most suitable solvent for UV spectroscopy is the one which does not absorb in the region
under investigation .
• Example: Ethanol, Hexane , Methanol , Cyclohexane etc.
• The position & intensity of absorption is affected by the polarity of the solvent.
• Following shifts are absorbed on changing the polarity of the solvents:
 Conjugated dienes and aromatic hydrocarbon experienced very little shifts on changing the polarity
of solvents.

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 The polar compounds show a change in absorption maximum on changing the polarity of the
solvent .
  unsaturated carbonyl compounds (ex: methyl vinyl ketone (butenone) or CH2 =CHCOCH3 )
show two different shifts on increasing the polarity of the solvent.

n → π* transition
• A net increase in energy required for a n → π* transition is thus
observed in protic solvents like water or alcohols.
• Increase in energy will reflect a decrease in wavelength.
• Hydrogen bonding stabilizes n more than * in polar solvents.
• Thus absorption band moves to shorter wavelength i.e. blue shift by
increasing the polarity of the solvent.

π → π* transition
• In the presence of a polar solvent , the more polar π* orbital will be more stabilized then π orbital
leading to a net decrease in the transition energy.
• The dipole –dipole interaction with the solvent molecules lower the energy of excited state more
than that of the ground state.
• Absorption band moves to longer wavelength i.e. red shift by increasing the polarity of the solvent.

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Q.8 Explain the instrumentation of UV-Visible Spectroscopy.

Ans. 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:
• The incident light of required wavelength is provided by different sources for different
spectroscopic technique.
• In ultra violet spectrometers the most commonly used radiation sources are –
 hydrogen discharge lamp
 deuterium lamp
 tungsten lamp
 mercury lamps .
• The sources of radiation must meet the following requirements:
a. It should be stable.
b. It should provide continuous radiation.
2. FILTER OR MONOCHROMATOR:
• For conversion of polychromatic radiation from source into monochromatic radiations, the devices
like filters or monochromators are used.
3. SAMPLE CONTAINERS OR SAMPLE CELLS
The sample is placed in the sample container which are cuvettes
Cuvettes:
• Cuvettes are generally made of quartz if work has to be done in ultra violet region.
• Cuvettes may be rectangular or cylindrical in shape .
Test Sample:
• The sample to be analyzed is placed between the detector and monochromator.
• The walls of the cell in which the test sample is placed should be transparent to the radiation used.

4. DECTECTORS:
• Detectors are used to measure accurately the absorption of an analyte via the intensity of the
transmitted light.

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Short Questions:

Q.a Explain the variation in the value of λmax for the following compound:
CH3 Cl λmax = 173 nm , CH3 Br λmax = 204 nm , CH3 I λmax = 258nm
Ans. All the compound undergo n →π* transition. As we move down the group , the quantum number
increases from Cl to I and hence the n electron lie far away from the nucleus. Thus these are easily excited
and λmax occur at higher value.

Q.b Most of the absorption band in UV-Visible spectra are very broad.Why?
Ans. The electronic transition in UV-Visible may take place with several vibrational and rotational energy
levels.

Practice Questions:
Q.(1) Which one of the following have higher λmax in U.V. spectroscopy.
(i) 1,3 pentadiene and 1,4 pentadiene
(ii) Anthracene and Benzene
(iii) CH3 COCH3 and CH2 =CH- CO- CH3

Q.(2) Identify the type of absorption n →π* , n →σ* & π → π* among the following compound.
a. CH3 COCH3 b. CH3 OH c. CH2 =CH2 d.CH2 =CH-CH=CH2

Q.(3) For a solution of camphor in hexane in a 10cm cell, the absorbance A was found to be 2.52 at
295nm with =14 . What is the conc. of camphor.

Q.(4) Acetone absorb at 279 nm in hexane whereas the values λmax in water is 264.5 nm. Explain.

Q.(5) Explain why polar solvent usually shift π → π* transition to longer wavelength and n → π*
transition to shorter wavelength .

Q.(6) Cis stilbene absorb at 274 nm and trans stilbene absorb at 294 nm. Explain.

Infrared Spectroscopy

Q.1 Explain the IR spectroscopy .

Ans. IR spectroscopy :
 IR spectroscopy deals with the infrared region of the electromagnetic radiation.
 It involves the transitions between vibrational energy levels.
 Infrared spectroscopy region lies between 4000-625 cm-1 (2.5-16 µm).
 Infrared spectroscopy (IR) measures the bond vibration frequencies in a molecule .

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 IR spectra can be used to provide information on the functional group as well as the structure of a
molecule.
Conditions for IR absorption
 The molecule must be show a change in dipole moment during vibration.
 The frequency of vibration of the molecule must be equal to the frequency of IR radiation.

Q.2 Explain the principle of IR spectroscopy and how vibrational frequency is related to the force
constant and reduced mass.
Ans. Principle of IR spectroscopy
 Molecules are made up of atoms linked by a chemical bonds.
 These bonds are analogous to springs and not rigid in nature.
 Because of the continuous motion of the molecule they maintain some vibrations with some
frequency characteristic to every portion of the molecule. This is called the natural frequency of vibration or
vibrational frequency .
 When energy in the form of infrared radiation is applied and when,
Infrared frequency= Vibrational frequency
This will lead to the generation of IR spectra.
The region where a stretching vibrational will occur in a molecule can be calculated by applying
Hooke’s Law, which is used for the motion of a spring.

Note : Vibrational frequency of a bond depends upon:

(i) Force constant which measure of bond strength .
For a single bond it is approximately 5 x 10 5 dyne cm-1 . For double and triple bond it becomes double and
triple respectively .Thus stronger the bond , greater will be the frequency of absorption.
(ii) Masses of the atoms involved in bonding or reduced mass. Thus greater the reduced mass, the lower is
the vibrational frequency.

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Q. 3 Define IR spectra. Why we get inverted peaks in IR spectra?

Ans. The plot of % Transmission of IR radiation versus wave number is known as IR spectrum.
While recording IR spectra ,% Transmission is plotted on y –axis and transmittance is inversely proportional
to absorbance [ A= -log T ],that’s why we get inverted peak.

Q.4 Classify the IR spectra or bands.

Ans. IR bands can be classified on the basis of their relative intensities in the IR Spectrum.
Strong (s)- A strong band cover most of the y-axis.
Medium (m)- A medium band fall to about half of the y-axis.
Weak (w)- A weak band falls to about one third or less of the y-axis.

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Q.5 What are the selection rules for Infrared transitions.

Ans. A selection rule describes the probability of transition from one level to another level.
Selection rules for Infrared transitions:
 For a particular vibration to be infrared active there must be a change in the dipole moment of the
molecule during the vibration .In other words transition dipole moment must not be zero.
 ∆ν= ±1, transition can take place between adjacent vibrational levels, 0 to 1, 1 to 2 etc.

Numerical Problems:

Q.a Calculate the approximate frequency of the C-H stretching for the force constant
5 x 10 5 dyne/cm.
Ans.

Note: atomic mass unit used to describe the mass of an atom. Thus
amu = Molar mass/Avogadro’s no.
Suppose in Question Force constant given in Nm-1
Newton is SI unit of Force = mass x acceleration
= kg x ms -2
1N = 1000 g x ms -2
Force constant 1 Nm-1 = 10 3 g s -2

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(Imp.)Q.6 Describe the various types of vibrations in IR spectroscopy .

Or Explain the fundamental mode of vibration for XY2 molecule .
Ans. Types of vibrations in IR spectroscopy:
(i) Stretching Vibration :- In this type of vibrations, the distance between two atoms increases or
decreases but the center atom remain in the same bond axis. During the stretching vibration , there is change
in bond length but no change in bond angle.

Types of Stretching Vibration :

(a) Symmetric Stretching: When the stretching and compressing occurs in a symmetric way, it is called
symmetric stretching.
(b) Asymmetric Stretching: When one bond is compressed and the other is stretched ,it is known as
asymmetric stretching.

(ii) Bending Vibration :- In this type of vibrations, the position of the atoms
changes with
respect to the
original bond axis
but the distance

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between the atoms remain same. In other words bond angle changes but the bond length remains same.

Types of Bending Vibration :

In plane Bending vibrations : In this type atoms remain in the same plane.

a) Rocking :-The mode of bending vibration in which both the atoms move to the same side and then
both move to the other side.

b) Scissoring :- The mode of bending vibration in which both the atoms approach each other.

Out plane Bending vibrations : In this type atoms remain in the different plane.

c) Twisting :- The mode of bending vibration in which one of the atoms moves up the plane while
the other moves down the plane with respect to the central atom.

d) Wagging:-The mode of bending vibration in which two atoms moves up

the plane and below the plane with respect to the central atom.

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Q.7 What do you mean by IR active and inactive molecules?

Ans. IR inactive molecules are those molecules that do not have either permanent dipole moment or
change in dipole moment during vibration.
Homonuclear diatomic molecules are IR inactive.
eg: H2 , O2 , N2 etc.
IR active molecules are those molecules, which undergo a net change in dipole moment during vibration.
Heteronuclear diatomic and polyatomic molecule are IR active.
eg:CO, NO, H2 O ,HCl etc.

Q.8 How fundamental vibrations are calculated.

Ans. The number of fundamental vibrations depend upon the structure of the molecule.
For linear molecules :
Vibrational degrees of freedom = 3N – 5
For Non-linear molecules:
Vibrational degrees of freedom = 3N – 6
where , N is the number of atoms in the molecule.
Example:
H2 O is non linear molecule. 3N – 6 = 3x3-6 = 3 fundamental vibrations.
HCN is linear molecule. 3N – 5 = 3x3-5 = 4 fundamental vibrations.

Q.9 Explain the fundamental vibrations of CO2 molecule.

Ans. CO 2 is linear molecule. 3N – 5 = 3x3-5 = 4.vibrations
It has expected four vibrational mode but actually three are considered.
Because in bending vibration ,there are two modes , but they have same frequency, so they are said to be
degenerate state. So out of 4 only 3 are consider as vibrational mode.
• The symmetric stretch does not result in a change (of the initially zero dipole moment), so it is IR-inactive.
• The asymmetric stretch does result in a change in dipole moment so it is IR-active.
• The bend also results in a change in dipole moment so it too is IR-active.

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Q.10 Write a short note on: (a) Functional-group region (b) finger print region.
Ans. (a) Functional-group region :
 Peaks in this region are characteristic of specific functional group.
 This region lies in between 4000 cm–1 to 1300 cm–1 .
 Different functional group absorb at characteristic frequencies in this region of the spectrum .
 Eg. OH- 3610-3650cm-1 , carbonyl CO- 1750 cm-1 , aromatic ring C-H -3000-3100 cm-1

(b) Fingerprint region:

 The area from 1300 cm–1 to 687 cm–1 is called the fingerprint region.
 The IR spectrum of an unknown substance compared with spectra of possible substance.
 The pattern of bands in this region are dependent on the structure of the molecule as a whole.
 Fingerprint region is associated with complex vibrational and rotational energy changes and is
characteristic of the molecule as a whole.

Q.11 Explain the factors affecting the vibrational frequencies.

Ans. Factors influencing vibrational frequencies: (i) Coupled Vibrations (ii) Electronic Effects
(iii)Hydrogen Bonding

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Vibrational coupling may take place between two bonds, through common atom , vibrating with similar
frequency. When the coupling is between two fundamental bands then it is called coupled vibration or
coupled band.

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Note:

Q.12 Explain the instrumentation of IR spectroscopy.

Ans. INSTRUMENTATION:
• A beam of infrared light is produced and split into two separate beams.
• One is passed through the sample, the other passed through a reference which is often the substance the
sample is dissolved in.
• The beams are both reflected back towards a detector, however first they pass through a splitter which
quickly alternates which of the
two beams enters the detector.
• The two signals are then compared
and a printout is obtained.
The IR instruments have following
parts:
1. IR source
2. Sample cell and sampling of
substances
3. Monochromators
4. Reference
5. Detector

Q.13 Write the applications of IR spectroscopy.

Ans. Applications of IR spectroscopy:
(1) Identification of functional groups.
(2) Determination of impurities in a sample.
(3) Determination of shape or symmetry of a molecule.
(4) Determination of force constant.

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(5) Provides a valuable information of dipole-moment, bond-lengths etc.

(6) Useful to distinguish positional isomers of a compound.
(7) Useful to distinguish between inter and intra molecular hydrogen bonding in a molecule.

Q.14 How do IR spectra help in differentiating the following compounds ?

(a) Aldehyde and Ketone
(b) Carboxylic acid and ester
Ans.

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Q.15 Why trans trichloroethylene shows no C=C stretching absorption while cis isomer show this
stretching.
Ans. The C=C bond in trans isomer is non polar having zero dipole moment. On stretching , the dipole
moment does not change and hence no absorption of IR radiation takes place.
Whereas cis isomer has a dipole moment , the magnitude of which increases on stretching and hence cis
isomer shows C=C stretching band. However both the isomer show bands for C-H and C-Cl stretchings.

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Practice Problems:
Q.a Calculate the approximate frequency of the C= N stretching for the force constant
103 Nm-1 . [ Ans. = 1619 cm-1 ]

Q.b Out of following pairs which one is expected to absorb at higher frequency for stretching
vibration. (a) C=C and C-C (b) O-H and C-C

Q.c Which of the following molecules has highest carbonyl stretching frequency.

Q.d How can you distinguish between intermolecular and intramolecular hydrogen bonding.

Q.e Two isomer A and B of the molecular formula C3 H6 O gives an IR absorption at 1650cm-1 and
1710 cm-1 Assign structure and formula to the isomers.

Q.f How is the force constant of a molecule related to the vibrational frequency.

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Rotational Spectroscopy
Q.1 Explain Rotational spectroscopy and write its application.
Ans. Rotational spectroscopy involves the transitions between the rotational energy levels of a gaseous
molecule having permanent dipole moment on the absorption of radiation falling in the spectral range of
1-100 cm-1 in microwave region.
Absorption of electromagnetic radiation /The coupling Mechanism
  
 The polar molecule start rotating A B if they have dipole moment, having (+) and (-)
charge during rotation, its electric field also rotate.
 At the same time if electromagnetic radiation interact with the rotating molecule .
 Then the frequency of microwave radiation match with the changing electric field frequency .
Frequency of microwave radiation = Frequency of changing electric field by the rotation of a
polar molecule
 Absorption of radiation takes place , during this condition transition takes place from ground state
to excited state, and we get rotation spectra.
 An electromagnetic wave is an oscillating field and interacts only with molecules that can undergo
a change in dipole moment.
 The oscillating dipole can be provided by the rotation of a permanent dipole like for example HCl
.This type of interaction leads to microwave spectra.

Fig. The rotation of a polar diatomic molecule, showing the fluctuation in the dipole moment
measured in a particular direction
Homonuclear diatomic molecules (such as H2 , O2 , N 2 , Cl2 ) :
 have zero dipole (non polar)
 have zero change of dipole during the rotation
 hence no interaction with radiation
 hence homonuclear diatomic molecules are microwave inactive.

Heteronuclear diatomic molecules (such as HCl, HF, CO,):

 have permanent dipole moment (polar compound)

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 change of dipole occurs during the rotation

 hence interaction with radiation takes place
 Therefore, heteronuclear diatomic molecules are microwave active.

Applications of Rotational spectroscopy:

(i) Determination of bond length of a polar molecule.
(ii) Determination of symmetry in a molecule.
(iii) Determination dipole moment of gaseous molecule.
(iv) Chemical analysis of a substance.

Q.2 What is microwave active and inactive molecules.

Ans. Molecules with permanent dipoles are microwave active. For a molecule to be microwave active
the molecule must be permanently polar .
For e.g. heteronuclear diatomic like HCl, CO, NO, etc. are microwave active while homonuclear
diatomics like O2 , N2 , etc. are microwave inactive.
The molecules with zero dipole moment are microwave inactive. In other words, a dipole must be
present in the molecule to get a rotational spectrum.

Note: The molecules with zero dipole moment are:

• H2 , O2 , N2 , Cl2 ,CS2, CO2, C2 H2 , BF3,CH4 , P4 , CCl4, NH4 +, XeF4 , SF4 , TeCl4 , SF6 , IF7 etc.

Q.3 Why rotational spectra is observed in gaseous state only.

Ans. Because in solid and liquid state rotational levels are not quantized.

Q.4 Explain rotational spectra.

Ans. In rotational spectra graph is plotted in between frequency and absorbance or wavenumber and
absorbance. The lines are nearly equally spaced and vary in intensity. Such spectra can be used to
determine bond lengths, and even bond angles in polyatomic molecules.

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Q.5 Describe an expression to calculate the rotational energy of rigid rotor model of microwave
active molecule.
Ans.

• Moment of inertia is used to calculate the rotational energy levels of rigid diatomic molecule .
• The rotational energy is quantized.
• By the using Schrödinger equation, the rotational energy levels allowed to the rigid diatomic
molecule are given by:

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Putting the value of J = 0,1,2,3,….. In above equation , the allowed rotational energy levels of a diatomic
molecule can be obtained as follows:

J 0 1 2 3 4 5 6
BJ (J + 1) cm-1 0 2B 6B 12B 20B 30B 42B

In pure rotational spectroscopy, the selection rule is ΔJ = ±1.

From the rule it is evident that only those transition are permitted in which there is an increase or decrease
by unity in the rotational quantum number.
In general , a transition taking place from J to J+1 .
Energy gap between two energy levels or rotational frequency between two energy levels :

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Q.6 How bond distance in polyatomic molecule are calculated in rotational spectroscopy.
Ans. Determination of bond length from rotational spectrum:
From the rotational spectrum ,which consists of series of equally spaced lines ,the value of B cab be

calculated as,

Q.8 Write the selection rule for rotational spectroscopy.

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 B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)

Ans. In pure rotational spectroscopy, the selection rule is ΔJ = ±1.

For absorption of radiation ΔJ = +1
For emission of radiation ΔJ = -1
From the rule it is evident that only those transition are permitted in which there is an increase or decrease
by unity in the rotational quantum number.

Q.9 Draw the instrumentation of rotational spectrometer.

Ans.

Practice Question:

Q.a Which of the following are microwave active molecules:

HF, O2 , CN, CH3 Cl, CO, H2 , C2 H2 , BF3, CH4 , H2 O ,NH3

Q.b Write the condition for microwave spectroscopy.

Q.a The pure rotational spectrum of gaseous HCl consists of a series of equally spaced lines
separated by 20.80 cm-1 .Calculate the internuclear distance of HCl molecule. [Ans.129pm]

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 B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)

Raman Spectroscopy

Q.1 What is the Raman spectroscopy.

Ans. In 1928 Sir C.V. Raman discovered that Raman spectroscopy.
 It is a type of spectroscopy which deals not with the absorption of electromagnetic radiation but
deals with the scattering of light by the molecules.
 When a beam of monochromatic light was allowed to pass through some organic substances, the
scattered light contained some additional frequencies over and above that of incident frequency .
This is known as Raman Effect.
 Raman spectroscopy can be defined as a spectroscopic technique base on inelastic scattering of
monochromatic light, usually from a laser source in the visible, near infrared and near ultra violet
range.

Q.2 Explain the Quantum theory of Raman Effect .

Ans. The occurrence of Raman scattering may be most easily understood in terms of the quantum theory
of radiation.
 This treats radiation of frequency  as consisting of a stream of particles (called photon) having energy
hwhere h is Planck’s constant. E = h
 When light interacts with matter, the photons which make up the light may be absorbed or scattered, or
may not interact with the material and may pass straight through it.
 When light is scattered by matter, almost all of the scattering is an elastic process, which means scattered
frequency is equal to the incident frequency and there is no change in energy this is called Rayleigh
scattering.
 Rayleigh Scattering : It is a elastic process ,which means scattered frequency is equal to the incident
frequency. ( s=i )
 However, a very small percentage of scattering is an inelastic process, thus a scattered light has different
energy from incident light. This inelastic scattering of light is called Raman scattering or Raman effect .

 Raman scattering can be classified as two types:

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(i) Stokes Raman scattering

 It is a process in which an electron is excited from the ground level and falls to a
vibrational level.
 The molecule thus absorb radiation with a lower frequency then the incident light.
 Such Raman scattered lines which are observed in the small frequency side are called
Stokes line. (  s < i )
(ii) Anti-Stokes Raman scattering
 It is a process in which an electron is excited from the vibrational level to the ground level.
 When the excited molecule returns to the ground state, it emits radiation which are of
higher frequency that the incident light.
 Such Raman scattered lines which are observed in the high frequency side are called anti-
Stokes lines. (  s >  i )

Figure 1. Diagram of the Rayleigh and Raman Scattering Processes

 Raman scattering is an extremely weak process and only one in 10 6 -108 photons scatters.
 This technique is highly sensitive.
 Rayleigh scattering is the dominant process.
 At room temperature , the intensity of stokes raman scattering is more than anti stokes Raman.
Because at room temperature , most of the electron exists at ground level.

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Raman Shift,  If  i represents the frequency of the incident radiation and  s light of scattered by a
molecular species ,then Raman Shift is

   i - s

For stroke’s line is positive.

For antistroke’s line is negative.

Conditions for Raman scattering

Raman spectroscopy is observed only when a molecule shows periodic change in polarizability due to
its vibrational or rotational oscillation.

Q. 3 Explain the raman selection rule.

Ans. Raman selection rules :
Raman spectroscopy is observed only when a molecule shows periodic change in polarizability due to
its vibrational or rotational oscillation.
For Rotational Raman:

 ΔJ = ± 2 ( rotational quantum number) (specific selection rule)

 In Raman, the rotational quantum number changes by two units rather than one because of
molecular polarizability.
 Thus the polarizability changes with a frequency which is twice the rotational frequency of the
molecule.
 For strokes lines = +2 and for antistokes lines = -2.

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For Vibrational Raman:

 Polarisability of molecule must change during a particular vibration (gross selection rule)
 Δv = ± 1 (vibrational quantum number) (specific selection rule)
 For strokes lines ,Δv = + 1 and for antistokes lines , Δv = - 1
Note:
 Hence all diatomic molecules, linear molecules and non-spherical molecules give Raman spectra
i.e. they are rotationally Raman active.
Ex: H2 , O2 , CH3 Cl , CH3 CH3, HCl ,H2 O, CH3 OH etc.

 On the other hand, spherically symmetric molecules such as CH4, SF6 , UF6 P4 , NH4 +etc. do not
give rotational Raman spectrum.They are rotationally Raman inactive. (These molecules are also
rotationally microwave inactive).

Q. 4 What do you mean by principle of mutual exclusion.

Ans.In a molecule with a center of symmetry it is seen that vibrations that are Raman active are IR
inactive and vice-versa, this is called the Principle of mutual exclusion (eg, as in CO 2 )

Q.5 Write the applications of Raman spectroscopy.

Ans. Applications of Raman spectroscopy:
i. Raman spectra provides a fingerprint by which molecule can be identified.
ii. It is used to detect explosives for airport security.
iii. It is used to discriminate between healthy and unhealthy tissues.
iv. It is used for the study of biological systems.
v. Raman spectra help to investigate the chemical composition of historical documents.

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Q.6 Write the difference between Raman and IR spectroscopy .

Ans.

Q.7Which of the following Spectroscopy (IR or Raman) would you use to measure the vibrational
frequency of the following bonds:
(i) Stretching frequency of 14 N - 15 N bond
(ii) C ≡ C stretch in ethylene (CH ≡ CH)
(iii) C=O stretch in acetone (CH3 COCH3 )
(iv) Re-Re stretch in compound (CO)5 Re – Re (CO)5

Ans.

(i) 14 N- 15 N : Homonuclear diatomic molecule; Non polar: IR Inactive as no change in dipole moment
during vibrations; Raman Active as change in polarizability takes place due to change in bond length.

(ii) C ≡ C stretch in CH ≡ CH; Symmetric molecule, Non polar: IR Inactive, Raman Active.

(iii) C=O stretch in acetone (CH3 COCH3 ): Polar bond ,change in dipole moment during vibration and
change in polarizability Thus IR and Raman both active.

(iv) Re-Re stretch in compound (CO)5 Re – Re (CO)5 : No polar bond , no change in dipole moment during
vibration. Thus IR Inactive, Raman Active.

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Q.8 Write the instrumentation of raman spectroscopy.

Ans. Raman Spectrophotometers all have the same basic components:
 A LASER source is needed to excite the target species.
 A filter collects the Raman scattered light (Stokes) and filters out the Raleigh and Anti Stokes
light.
 A diffraction grating bends the Raman shifted light according to wavelength.
 A detector records the signal and passes the signal to a computer for decoding.

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