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

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

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

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

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

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

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.

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