DR.DIGAMBAR D.

GAIKWAD
DEPT. OF CHEMISTRY,
GOVT. COLLEGE OF ARTS & SCIENCE,
AURANGABAD-431001
E-mail:-gaikwad_dd@yahoo.com
Mobile No. 9422552449
------------------------------------------------------------------------------------------------------------

CHAPTER 3. ELECTRONIC SPECTROSCOPY

The spectroscopy deals with study of electromagnetic radiation with matter. Thus
it gives the information about the transition between rotational and vibrational energy
levels with the addition of electronic transition. In this technique the matters come in
contact with different types of radiations such as such as UV, Visible, Micro-wave,
Radio-waves produce different kinds of excitations of the molecules and this excitation
provides important information about the structure of molecules and atoms. This
information given by the molecule are recorded with the help of a device
Spectrophotometer, in the form of a graph also known as Spectrum. A molecule exposed
to radiation absorbs part of it and gets excited to higher energy level. The type of
wavelength of radiation absorbed by the molecule in order to reach the state depends
upon the structural features of the molecule. By studying the spectrum technique
obtained, it is possible to throw light on the chemical constitution of the molecules. The
spectroscopy can be studded by following two basic points
i) Atomic spectroscopy:- This spectroscopy is concerned with the
interaction of electromagnetic radiation with atoms which are commonly
in their lowest energy states
ii) Molecular spectroscopy:-This spectroscopy deals with interaction of
electromagnetic radiation with molecules.

Fig. 3.1 Propagation of electromagnetic radiation

Where
X →Axis of propagation of radiation
Y → Axis represents direction of magnetic field
Z → Axis represents direction of electric field.

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 Thus results in transition between rotational and vibrational energy levels in
addition to electronic transitions. Spectroscopy is, therefore, the study of molecular
responses when it is exposed to certain kind of radiations.
The absorption of different types of radiations such as UV, Visible, Micro-wave,
Radio-waves produce different kinds of excitations of the molecules and this excitation
provides important information about the structure of molecules. Since in these methods
the nature of radiation absorbed is studied, the Spectroscopic methods designated as
absorption Spectroscopy (The Ultra-Violet region, which extends from 200-400 nm and
the visible ranging from 400-800 nm)
In absorption Spectroscopy, the molecule has different kinds of radiations.
Therefore it is necessary to study the properties of radiations. Electromagnetic radiations
has dual nature i.e. particle and wave form. In studying Spectroscopy more importance is
given on wave form of the radiation. Radiations when propagate in wave form produce
electric and magnetic fields. The directions of their propagation are mutually
perpendicular to each other as shown in the above fig. (1).

The electromagnetic wave are characterized by following parameters

1. Amplitude (a)
2. Energy (E)
3. Wave length (λ)
4. Frequency (γ)
5. Wave number (υ)
The units commonly used for the following parameters are as fallows
Wave length (λ):-It is the distance between two successive maxima on an
electromagnetic waves
1 A° (Angstrom) 10-8 cm = 10-10 m
1 nm (Nanometer) 10-7 cm = 10-9 m
1 µ (Micron) 10-4 cm = 10-6 m
Frequency (γ):- The number of wavelength units passing through a given points
in unit time is called as the frequency
1Hz (Hertz) = 1 Cycle per second (cps)
1 KHz (Kilo Hertz) = 103 Hertz
6
1MHz = 10 Hertz
Wave number (ν):- The frequency as the wave number which is defined as the
number of waves per centimeter in vacuum. This quantity is generally denoted by ν
The measured in term of number of waves/cm = cm-1 or Kaysers (K)
1 kayser = 1 cm-1
The spectrum, of electromagnetic radiation is shown in bellow with increasing
wavelengths or decreasing frequencies.

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Cosmic Y - X- UV Visible IR Micro Radar TV Radio
ray ray wave

nm 10-5 10-3 0.1 100 400 800 103 107 109 1010 1011
High energy Low E

Energy(E)

Fig. 3. 2 Electromagnetic spectrum.

The visible portion is shown on an expanded scale

Wavelength (λ)

Types of radiations according to wavelength Table No. 1

The above table shows that, cosmic rays have the shortest wavelengths and
highest energy similarly radio waves have the longest wavelengths and lowest energy. As
we move from left hand side to right hand side in the above table the wavelength goes on
increasing at the same time energy and frequency go on decreasing. The visible region
lies between Infra- red and Ultra -violet region. Although all types of radiations travel as
waves with same velocity but they differ from one another in certain properties for
example, X - rays can pass through glass and muscle tissues. Radio waves pass through

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air. Visible and Infra-fed radiation can be sent by reflection or diffraction in a prism, it is
observed that when radiation of certain frequency and energy (ΔE=hυ) are passed
through an organic compound, the electrons of the component atoms are excited. In
addition the vibrational and rotational energies of the molecules as a whole are quantized.
The wavelength are measured and recorded in the form of a spectrum with the help of a
device called Spectrophotometer. If we plot the changes in absorption against
wavelength, we get absorption bands which are highly characteristic of a compound and
the technique provides an excellent tool to elucidate the molecular structure of an
unknown compound. Interaction of radiation with Matter when radiation strikes the
matter, the molecule absorbs part of it. The wavelength or frequency of radiation
absorbed depends on the structural features of molecules. As a result of absorption of
energy, molecule undergoes excitation higher energy state. The type of excitation
produced depends upon the energy of the radiation used.
i. Rotational excitations:- These excitations occur if microwaves are used (λ= 105
to 107 nm)
ii. Vibrational excitations:- These excitations occur if IR radiations are used. Since
the energy of IR radiation is higher than microwave (800 – 10-5) along with
vibrational excitations, rotational excitation also takes place.
iii. Electronic excitations:- These excitations occur if the radiations from Visible
and UV region are used; they bring about electronic excitations from bonding
and anti-bonding levels. As energy of these radiations is higher than IR
radiations, along with electronic excitations, vibrational and rotational excitations
also take place.
Microwaves = Rotational excitations
Infrared = Vibrational + Rotational excitations
UV and Visible = Electronic + Vibrational + Rotational excitations
In the study of spectroscopy, the molecule is exposed to the various types of
radiations. The wavelength of the radiation slowly changed from minimum to maximum
in the given region and the absorption at every wave length is recorded. A graph
wavelength vs absorbance is then plotted.

Fig. 3.3 Graph of wavelength vs Absorbance

Above graph shows that the absorption is maximum at a particular wavelength.
The wavelength at which there is maximum absorption observed is called as wavelength

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maximum. This is a characteristic property of the molecule and helps in determining its
structure.
Ultraviolet and Visible Spectroscopy
These are given following regions
Vacuum Ultraviolet 1-180nm
Ultraviolet 180-400nm
Visible 400-750nm
The Ultra violet region, which extends from 180-400 nm and the visible region
from 400-75nm are more useful to organic chemists. They bring about electronic
excitations in the molecule from bonding to anti-bonding levels. Information about the
structure of the molecule containing double bond or triple bond or conjugated bonds is
given by UV-Visible spectroscopy. It also helps in differenting conjugated and isolated
dienes, carbonyl compounds and α, β unsaturated carbonyl compounds and cis and trans
isomers. Since the energy level of a molecule is quantized, the energy required to bring
about the excitation is a fixed quantity. Thus, the electromagnetic radiation with only a
particular value of frequency will be able to cause excitation. Allowed to fall on sample
of the molecule, energy is absorbed and electrons will be promoted to the higher energy
levels.
Beer - Lambert law
The Beer-Lambert law is the linear relationship between absorbance and
concentration of an absorbing species. This law states that, "The fraction of the incident
light absorbed is proportional to the number of molecules and the path of light that is
absorbed by the solution which is proportional to its concentration. The absorbance of
light is directly proportional to the thickness of the media through which the light is being
transmitted multiplied by the concentration of absorbing chromospheres.

This law states that

Log Io = ξ x C x L
It
Where
Io=Intensity of incident light
It = Intensity of transmitted light
A = Absorbance
ξ = Extension coefficient
C = Concentration of solution (ml)
L = Length of the cell (cm)

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 The UV spectra are usually recorded as absorption (A) vs wavelength (λ). The
intensity of peak is found by plotting ξ or log ξ vs wavelength. The intensity of
absorption depends upon following two things
i) Size of the molecule
ii) Change in dipole moment
Spectrophotometer:-
The device which detects the percentage transmittance of light radiation when
light of certain intensity and frequency range is passed through the sample. The modem
UV-Visible spectrophotometer consists of following components
i. Radiation source:- A deuterium or hydrogen lamps discharge of the range
180-400 nm or tungsten filament lamp of wavelength greater than 375 nm
are used as radiation source.
ii. Sample container:- It is a quartz or fused silica transparent cell of 1 cm
path length. (Glass cell cannot be used as glass absorbs light strongly below
300 nm).
iii. Monochromator:- The incident radiation is dispersed with the help of a
rotating prism and wavelengths thus separated are passed through a
specially devised slit to a monochromatic beam of desired wavelength. It is
then divided into two beams of equal intensity. Thus light from the first
dispersion is passed through a slit called Monochromator and then sent to
second dispersion, light passes through the exit slit.
iv. Detector:- In Spectrometer the reference beam subtracts the absorption of
the solvent from the absorption of the solution. The signed for the intensity
of absorbance Vs corresponding wavelength is automatically recorded on the
graph with the help of detector.
v. Amplifier: The amplifier is coupled to a small servomotor, which drives an
optical wedge into the reference beam until the Photoelectric cell receives
light of equal intensities from the sample as well as reference beams.
vi. Recorder:- Amplifier is also coupled with a small servomotor which in turn
is coupled to a pen recorder. It records the absorption bands automatically.
vii. Sample and Solvent:- It is essential that a spectrum should be recorded in
dilute solutions and solvent must be transparent within the range of
wavelength being examined. Only 0.1 mg of pure and dry sample is dissolved
in about 100 ml non absorbing solvent like cyclohexane, 1, 4-dioxane, water
or 95% ethyl alcohol. (Absolute alcohol cannot be used as it contains traces of
benzene which shows peak at 225 nm). Sometimes a sample in pure gaseous
state may be used.

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 Fig. 3.4 Ultraviolet Spectrophotometer
Working
One of the beams of selected monochromatic light is passed through the sample
solution and the other beam of equal intensity is passed through the reference solvent.
The intensities of the respective transmitted beams are then compared over the whole
wavelength range of the instrument. The spectrophotometer electronically subtracts the
absorption of the solvent in the reference beam from the absorption of the solution. The
signal for the intensity of absorbance versus corresponding wavelength is automatically
recorded on the graph. The spectrum is usually plotted as absorbance (A) against
wavelength (λ).

Types of Electronic Transitions

UV - Visible radiations are more energetic. Absorption of these radiations by an organic
compound brings about electronic excitations. The process of electronic excitation is
accompanied by a large number of vibrational and still larger numbers of rotational
changes.
E = E electronic + E vibrational + E rotational

Fig. 3.5 Energy levels diagram

There are three kinds of electrons present in organic molecule viz.
i) σ- electrons present in Sigma bonds
ii) π - electrons present in pi bonds
iii) n - nonbonding electrons present as unshared electrons

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 Fig. 3.6 Electronic transitions
The amount of ultraviolet radiation absorbed depends upon the structure of the
compounds and their wavelength of radiation. The following types of electronic
transitions.
1. σ →σ* Transition:
The electron is excited from bonding to anti-bonding orbital that is σ
→σ* Transition. High energy is required for this transition as sigma (σ ) bonds
are very strong. This transition accurse at shorter wavelength that is 165nm such
as saturated hydrocarbon like CH4, CH3CH3

6 6*
C C C C

2. π → π * Transition:
The excitation of electron from bonding (π ) to an anti-bonding (π *)
orbital. This transition occurs in compounds containing double or triple bonds.
e.g. Alkenes, Alkynes, Carbonyl and Cyanides compounds etc. Such transitions
requires comparatively less energy than that required for n →σ* transitions and
conjugation of double bonds lowers the energy required for the transition and
absorption occurs at longer wavelengths.

C C C C

3. n →σ* Transition:
When one electron from nonbonding lone pair to anti-bonding orbital
that is n →σ* Transition. This type of transition occurs with compounds
containing single or double bonds containing heteroatom like O, N and S atoms.
This transition contain lower energy than σ →σ* Transition.

C X C X

e.g. Alcoholes, Aldehyde, Ketones, Eters and Amines etc.

4. n → π * Transition:

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 It represents the Transition of one electron of a lone pair to an anti-
bonding orbital. Thus transition require lower energy than compared to π→ π *
transition and hence absorbance occur at longer wavelength. Compound
containing hetroatom gives this type of transition such as CN, CO, CS, NO etc.

C O C O

The decreasing order of energy required for these transitions can be represented as

σ →σ* > n →σ* > π → π * > n → π *

Transition probability:
It is not necessary that when a compound absorbs UV light, there will be
promotion of an electron from bonding or lone pair to an ant-bonding or non-bonding
orbital. The probability of a particular electronic transition is found to depend on the
value of molar extinction coefficient.
The extinction coefficient
ξmax = 0.87 x 1020 p.a.
Where
p = Transition probability with values from 0 to 1
a = Target area of the absorbing system
It is observed that the value of ξmax is found to be around 105 when the
chromophore has a wavelength of the order 10A0 or 10-7cm. The chromophore with low
transition probability will be having ξmax < 1000. Hence there is a direct relationship
between the area of the chromophore and the absorption intensity ξmax. In addition there
are some other important factors which give their impact on transition probability.
Depending upon the symmetry and the value of ξmax, the transition may be classified as
allowed and forbidden.
i. Allowed transition: The transition with the values of Extinction coefficient (ξ
max) more than 104 are usually called allowed transitions.
e.g.
π → π * transitions in 1, 3 butadiene (217 mm ξ max 22,000).
ii. Forbidden transitions: The forbidden transition is a result of the excitation of
one electron from the loan pair present on the hetero atom to an ant-bonding π *
orbital. The values of ξmax for forbidden transitions are generally below 104.
e.g.
n → π *transition in carbonyl compounds (ξmax. 10-100)
In order to decide whether the transition is allowed or forbidden for symmetrical and
totally unsymmetrical molecules, it is important to consider following factors:
a. Geometry of the molecular orbital in the ground state
b. Geometry of the molecular orbital in the excited state
c. Orientation of the electric dipole of the incident light that might induce transition
Terms used in UV spectra

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Following four terms are used
1. Chromophore:-
Chromophore was considered as any system which is responsible for imparting
colour to the compound. Nitro group is the chromophore which imparts yellow colour.
The term chromophore may be defined as any isolated covalently bonded group that
shows a characteristic absorption in the UV or Visible region.
The origin of this word comes from the Greek that is Chroma means colour and
Phoros means bearing. So chromophore means colour bearing unit of the molecule e.g.
Ethylenic, Acetylenic, Carbonyls, Acids, Esters group etc. Carbonyls, group is an
important chromosphere although the absorption of light by an isolated group does not
produce any colour in UV spectroscopy. There are two types of chromophore 1) The
chromophore which contain π electrons and they under go n → π * e.g. Ethylene,
Acetylene 2) The chromophore which contain both n and π electrons such chromophore
undergo two types of transition n → π * and π → π * e.g, Carbonyls, Nitriles, Azo
compound, Nitro compounds etc.
2. Auxochrome:-
An auxochrome can be defined as any group which does not itself acts as a
chromophore but whose presence brings about a shift of the absorption band towards the
red end of the spectrum. Asoption at longer wavelength is due to combination of
chromophore an as auxochrome gives rise to another chromophore. An auxochromic
group is called as colour enhancing group e.g. -OH, -OR, -NH2, -NHR, -NR2, -SH etc.

Aniline λ max = 280nm

(ξmax = 1430)
The effect of auxochromic group is due to its ability to extend the conjugation of
a chromophore by the sharing of non bonding electrons. Thus a new chromophore results
which has different value of absorption maximum as well as extinction coefficient.
3. Bathochromic Shift (Red Shift)
Absorption due to auxochrome or by the change of solvent towards longer
wavelength is known as Bathochromic shift or red shift. The n → π * transition for
carbonyl compound gives bathochromic shift when the polarity of solvent is decrease.

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 O O O O
N N

Alkaline OH-
H+

OH O
I II
λ max = 255nm λ max = 265nm
(ξmax = 900) (ξmax = 150000)

P-Nitrophenol
The negatively charge present on oxygen atom delocalized more due to red shift.
4. Hypsochromic shift (Blue shift)
It is an effect in which the absorption is shifted towards shorter wavelength. It
may be caused by the removal of conjugation and also by changing the polarity of the
solvent. e.g. Aniline shows blue shift in acidic medium and an unshared pair on nitrogen
of aniline is not available for delocalization in cation.

NH2 NH3Cl

HCl

λ max = 230nm λ max = 262nm

5. Hyperchromic shift
Absorption of electromagnetic radiations having greater intensity is called
hyperchromic shift .
e.g.. Pyridine and 2-methyl pyridine

HCl

N N CH3
λ max = 257nm λ max = 262nm
(ξmax = 2750) (ξmax = 3560)
The introduction of an auxochrome usually increase intensity of absorption.
6. Hypochromic shift
Absorption of electromagnetic radiation having lesser intensity is called
hypochromic shift. The presence of extra group which destroy the geometry of the
molecule cause the hypochromic effect.

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 CH3

λ max = 250nm λ max = 237nm

(ξmax = 19000) (ξmax = 10250)

Fig. 3.7: Absorption and intensity shifts

Effect of solvent on UV spectra:
The polarity of solvent also affects the various types of band in compounds
a. K* Bands:-
This type of bands occurred due to π → π * transition takes
place compounds containing conjugated system of bonds such as dienes,
polynes and enones etc. The intensity of this bands more than 104.
Butadiene π → π * transition 226nm (λmax)
Acetophenone π → π * transition 224nm (λmax)
b. R*Bands:-
This bands also called as fprbiden bands.This type of bands
occurred due to n→ π * transition takes place compounds containing
single chromophoric groups and at least one lone pair of electron the
heteroatom such as N, O and S. These are less intensity with ξmax values
below of these bands more than 104.
Aldehyde n→ π * transition 293nm (λmax)
Ketone n→ π * transition 270nm (λmax)
c. B-Bands:-
This type of band is formed due to π → π * transition in
aromatic compound chromophoric group or hetero - aromatic compound.
The observed wavelength and intense less than K - band.
Acetophenone π → π * transition 278nm (λmax)

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 Benzaldehyde π → π * transition 280nm (λmax)
d. E-Bands:-
This band is formed due to electronic transition in the benzenoid
system of three ethylenic bonds which are related to cylic conjugation.
This band given as two types E1-bands & E2-bands.
Compounds E1-bands (λmax) E2-bands (λmax)
Benzene 184nm 204nm
Napthalene 221nm 286nm
Anthracene 256nm 375nm
Quinoline 288nm 270nm.

UV Spectra of Aromatic Compound:-

As the conjugation in the compound increases, the λmax and ξ max value also
get shifted to higher value i.e. Bathochromic and Hyperchromic effect are observed.
While studying the series of aromatic compounds like Benzene, Naphthalene, Anthacene,
Phenanthrene, etc the increase in aromaticity or conjugation increases the Bathochromic
and Hyperchromic effect. Benzene absorbs at 184nm; 60,000 ξ max, 204nm; ξ max
7400 with allowed transition and shows B-band at 254 nm with ξ max 204 i.e. Forbidden
transition. Benzene also shows intensity band between 230 and 270nm.The B-band at
254nm given by benzene is fineness structure in hexane solvents while in alcohol it is
completely destroyed. It is noted that absorption maxima for Poly-nuclear aromatic
hydrocarbon moves to longer wavelength. While comparing the UV spectra of benzene
with other aromatic compounds shows increase in the value of λmax and ξmax.

Absorption of Aromatic Compound:

S.N. Compound λmax)nm) ξmax Transition.
Name

1 Benzene 184 60,000 Allowed

204 7400 Allowed

254 204 Forbidden

2 Naphthalene 480 11,000

3 Pentacene 580 12600

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Woodward - Fischer Rules:-
In 1945 Robert Burns woodward gave certain rules for correlating (λmax) with
molecular structure. In 1959 Louis Frederic Fieser modified these rules and the modified
rule is known as Woodward-Feiser rules. It is used to calculate the position and λmax) for
a given structure by relating the position and degree of substitution of chromophore. Each
type of diene or triene system is having a certain fixed value at which absorption takes
place, this constitute the base value or parent value. This rule state that it is used for
finding absorption maxima (λmax) in an ultraviolet–visible spectrum of a given
compound. Longer the conjugated system grater is the wavelength of absorption
maximum. The intensity of absorption also increases with the increase in the lenth of the
chromophore. This is used in the calculation are the type of chromophores present, the
substituents on the chromophores and shifts due to the solvent. Examples are conjugated
carbonyl compounds, conjugated dienes and polyenes.
Double bond conjugation diene correlation described as fallows
a. Alicyclic or Open chain diene:-In chemistry, an open-chain compound
or acyclic compound is a compound with a linear structure, rather than a
cyclic one. An open-chain compound having no side chains is called a
straight-chain compound.
H
H2C C
C CH2
H
b. Homo-anular diene:-Cyclic diene having conjugated double bond in the
same ring.

c. Hetro-annular diene:- Cyclic diene having conjugated double bond in

the different ring.

d. Endo-cyclic double bonds:- Double bond present in the ring

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 e. Exo-cyclic double bonds:-Double bond in which one of the doubly
bonded atoms is a part of ring system. Here first ring has one exocyclic
and endocyclic double bond. Second ring has only one endocylic double
bond.

Parent value and increments for different groups and substituents:

 Parent Value
a) Butadiene or cyclic conjugated butadiene 217 nm
b) Acyclic triene 245 nm
c) Homoannular conjugated diene 253 nm
d) Heteroannular conjugated diene 215nm
 Increments for substitution
a) Alkyl substituents 5 nm
b) Ring residue 5 nm
c) Exocyclic double bond 5 nm
d) Double bond extending conjugation 30nm
e) Bicyclic or strain correction 15 nm
 Auxochrome
-Cl,-Br +5nm
-OR +6nm
-SR +30 nm
-NR2 +60 nm
-OCOCH3 0 nm
 If the cyclic diene or open chain conjugated diene is substituted by -Cl or -Br
then 17nm is added in basic value.
 The difference between calculated value and observed value of (λmax) should be
lower than 5 nm.
Woodward - Fischer Rules for calculating (λmax) in α, β carbonyl compounds
Woodward Fischer suggested some empirical rule for the calculation of λmax) in α, β
unsaturated compound, which was modified by Scott, which are as follows
 In α, β unsaturated ketone is taken as 215mμ.
 In a cyclic ketone, if α, β unsaturated carbonyl group is a part of six member
cyclic ring then basic value is taken as a 215 nm, but if α, β unsaturated carbonyl
group is a part of five member ring then base value is taken as 202 nm. The (λmax)
for such compounds are generally 104
Structural increments for calculation of (λmax) for given α, β unsaturated carbonyl
compound
1) Exo-cyclic double bond +5 nm
2) For each double bond extending conjugation +30 nm
3) For a homo-anular conjugated diene +39 nm

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4) For each double bond endocyclic. +5nm
5) Increment of various auxochrome:
Chromophore α β γ δ

Ring residue +10 +12 +18 +18

-R +10 +12 +18 +18
-OR +35 +30 +17 +31
-OH +35 +30 - +50
-OCH3 +6 +6 +6 +6
-Cl +15 +12 - -
-Br +25 +35 - -
-SR - +85 - -
-NR2 - +95 - -

Application of Woodward - Fischer Rules to calculate (λmax) of the following

compounds
1. Calculate (λmax) for the given structure

O
H3C

C CH C CH3

H3C
Ans:
The above given compound is α, β-unsaturated ketone
Basic value = 215 mµ
2 alkyl β-substituent (2x12) = 24 mµ
---------
Calculated value = 239 mµ

2. Calculate (λmax) for the given structure

CH3 O

H2C C C CH3
Ans:
The above given compound is α, β-unsaturated ketone
Basic value = 215 mµ
1 alkyl substituent = 10 mµ
------------

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 Calculated value = 225 mµ

3. Calculate (λmax) for the given structure

CH3
CH3
H3C

Ans:
The above given compound is homoannular conjugated diene
Basic value = 253mµ
3 Ring residues (3x5) = 15mµ
1 exo-cyclic double bond = 05mµ
----------
Calculated value = 273 mµ

4. Calculate (λmax) for the given compound

CH3
CH3
CH3

Ans:
The above given compound is heteroannular conjugated diene
Basic value = 215mµ
3 Ring residues (3x5) = 15mµ
1 exo-cyclic double bond = 05mµ
----------
Calculated value 235 mµ

5. Calculate (λmax) for the given compound

Ans:
The above given compound is heteroannular conjugated diene
Basic value = 215mµ
4 Ring residues (4x5) = 20mµ
----------
Calculated value = 235 mµ

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6. Calculate (λmax) for the given compound

CH3

Ans:
The above given compound is heteroannular conjugated diene
Basic value = 215mµ
3 Ring residues (3x5) = 15mµ
1 exo-cyclic double bond = 05mµ
----------
Calculated value = 235mµ

7. Calculate (λmax) for the given compound

CH3

H3C

O
Ans:
The above given compound is homoannular α, β-unsaturated ketone
Basic value = 215mµ
1 α-ring residues = 10mµ
1 δ-ring residues = 18mµ
1 exo-cyclic double bond = 05mµ
1 double bond in conjugation = 30mµ
1 homoanular conjugated diene = 39mµ
----------
Calculated value = 317mµ

8. Calculate (λmax) for the given compound

O

Ans:
The above given compound is α, β-unsaturated cyclic ketone
Basic value = 215mµ

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 1 α-ring residues = 10mµ
2 β-ring residues(2x12) = 24mµ
double bond exocyclic to two ring (2x5) = 10mµ
----------
Calculated value = 259mµ

9. Calculate (λmax) for the given compound

CH3

H3C CH3

Ans:
The above given compound is homoannular diene
Basic value = 253mµ
4 alkyl residues (4x5) = 20mµ
----------
Calculated value = 273mµ

10. Calculate (λmax) for the given compound

CH3

CH3
Ans:
The above given compound is homoannular diene
Basic value = 253mµ
3 alkyl residues (3x5) = 15mµ
----------
Calculated value = 268mµ

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B. INFRA-RED SPECTROSC0PY
Infrared spectroscopy is one of the important spectroscopic techniques for the
detection of functional groups in pure unknown organic compounds. The infrared
electromagnetic spectrum can be divided into following type
Near IR region 0.8 μm - 2.5 μm
IR region 2.5 μm - 15 μm
Far IR region 15 μm - 200 μrn
The absorption of IR radiation are expressed in terms of wavelength (λ).
Different functional groups absorb characteristic frequencies of IR radiation. Thus, IR
spectroscopy is an important and popular tool for structural elucidation and compound
identification. In this electromagnetic spectrum, that is light with a longer wavelength and
lower frequency than visible light. As with all spectroscopic techniques, it can be used to
identify and study chemicals. A common laboratory instrument that uses this technique is
a Fourier transform infrared (FTIR) Spectrometer. The higher-energy near-IR,
approximately 14000–4000 cm−1 (0.8–2.5 μm wavelength) can excite overtone or
harmonic vibrations. The mid-infrared, approximately 4000–400 cm−1 (2.5–25 μm) may
be used to study the fundamental vibrations and associated rotational-vibrational
structure. The far-infrared, approximately 400–10 cm−1 (25–1000 μm), lying adjacent to
the microwave region, has low energy and may be used for rotational spectroscopy. The
names and classifications of these sub regions are conventions, and are only loosely
based on the relative molecular or electromagnetic properties
IR spectrum gives detailed information about the functional groups present in
the given organic compound and spectrum obtained within 3 to 7 minutes and requires 4
to 5 mg of the sample which can be recovered.
Principle of IR spectroscopy
The absorption of IR radiations causes an excitation of molecule from lower
vibrational level to higher vibrational level. But as the vibrational level is associated with
a number of closely spaced rotational levels, the IR spectra is considered as vibrational -
rotational spectra. The necessary condition for the molecule to absorb in IR region is to
change in dipole moment. In general, vibrational transitions which will lead to a change
in the dipole moment of the molecule are called IR active transitions. Otherwise they are
said to be IR inactive and will show no absorption. For ex. Vibrational transition in H 2,
N2, Cl2 do not results in a change in dipole moment of a molecule. Hence these molecules
are not absorbed in IR and are called as IR inactive. But Vibrational transition in I-CI,
CO, CHCl3 results in a change in dipole moment of a molecule. Hence these molecules
are absorbed in IR and are called as IR active. Electromagnetic radiation of IR region is
absorbed to various extents by all substances. The absorption process involves excitation
of the molecule to higher vibrational states and therefore is quantized. Even at 0° K the
atomic nuclei are vibrating about the bond which binds them together.
Presentation of the IR spectra
The IR radiation does not have sufficient energy to cause the excitation of
electrons. However it causes atoms and groups of atoms of organic compounds to vibrate
faster about the covalent bonds which connect them. The vibrations are quantized and as

Page 20 of 38
they occur, the compound absorbs IR energy in particular regions of the spectrum. The
position of an absorption band can be specified by following units,
1. Frequency (γ) - nm or cm-1 or Hz.
2. Wavelength (λ) -µm (1 μm = 10-4 cm).
3. Wave numbe(υ ) -cm-1
v = 1/λ, (with λ in cm)
v = 10,000/λ (with λ in μm)
An IR spectrum is the graph of, % transmittance vs increasing wavelength or decreasing
frequency. Each spectrum called a band or peak represents absorption of IR radiation at
that frequency by the sample. A 100% transmittance means 0% absorption and if all the
radiation is absorbed, the transmittance is 0%.

Fig.3.13. Regions in the IR spectrum

Radiation source: The various popular sources of IR radiations are:
1. Incandescent lamp: In the Near IR instruments an ordinary incandescent lamp is
generally used. However, this fails in the Far IR because it is glass enclosed and has a
low spectral emissivity.
2. Nernst Glower: It consists of a hollow rod which is about 2 mm in diameter and 30
mm in length. The glower is composed of rare earth oxides such as Zirconium, Yttrium
and Thorium. Nernst Glower is non-conducting at room temperature and must be heated
by external means to bring it to a conducting state. Glower is generally heated to a
temperature between 1000-1800 °C. It provides maximum radiation at about 7100 cm-1
(1.4 μm).
The main disadvantage of Nernst Glower is that it emits IR radiation over a wide
wavelength range; the intensity of radiation remains steady and constant over long
periods of time. One main disadvantage of Nernst Glower is its frequent mechanical
failure. Another disadvantage is that its energy is also concentrated in the visible and
Near IR regions of the spectrum.
90
3. Globar source: It is a rod of centered silicon carbide which is about 50 mm in length
and 4 mm in diameter. When it is heated to temperature between 1300 and 1700 °C, it
strongly emits radiation in the IR region. It emits maximum radiation at 5200
cm"1.Unlike the Nernst Glower, it is self-starting. As its temperature coefficient is
positive, it can be conveniently controlled with a variable transformer. It also works at
wavelengths longer than 650 cm-1.The main disadvantage is that it is a less intense source
than the Nernst Glower.
4. Mercury Arc: In the Far IR instruments, high pressure Mercury Arc is generally
employed. Beckmann devised the quartz mercury lamps for the same region in a unique

Page 21 of 38
manner. At the shorter wavelengths, the heated quartz envelope emits the radiation
whereas at the longer wavelengths the mercury plasma provides radiation through the
quartz.
Types of vibrational modes
The atoms in a molecule are not rigid but elastic. Covalent bond between atoms
show like a spring. When Infrared radiation is passed through organic compounds
vibrational and rotational energies of the molecule get increased. A nonlinear molecule
undergoes two kinds of fundamental vibration.
a) Stretching vibrations: The change in the internuclear distance between two atoms
without changing bond axis is called stretching vibration. In this distance between two
atoms increases or decreases. These vibration are further divided into two types
i) Symmetrical stretching: In this type the movement of atoms is in the same
direction with respect to particular reference atom.

ii) Asymmetric stretching: In this type of vibration, the movement of a atom

is towards to the centre while that of another atom is opposite to centre
with respect to particular reference atom.

b) Bending vibrations: The change in angle between two covalent bonds, due to
change in the position of atoms with respect to the original bond axis is called as bending
vibrations. There are four types of bending vibrations,
a) In plane bending vibration
i) Scissoring:
In this type, two atoms approach each other with respect to central atom.

Page 22 of 38
ii) Rocking:
In this type, the movement of atoms takes place in the same direction
with respect to central atom,

b) Out of plane bending

i) Wagging:
In this type, two atoms move "up and down" the plane with respect to
central atom,
(+)

(-)

ii) Twisting:
In this type, one of the atom moves up the plane while the other moves
down the plane with respect to central atom.
(+)

(+)

Bending vibration is more as compared to stretching vibration and requires less

energy. Hence bending vibration occurs at higher wavelengths than stretching.

Page 23 of 38
Hooks Law:-
This law first discovered by Robert Hooke the 17th century physicist who
discovered it in 1660 Hooke’s Law. This law gives the relationship between the forces
applied to a spring and its elasticity. The value of stretching vibrational frequency of a
bond can be calculated by the application of Hooks law which is expressed as fallows
k
m1 m2

1/2π

µ = m1m2
m1+m2
Where
k -Force constant
γ -Frequency
μ -Reduced mass
m1 -mass of first atom
m2 -mass of second atom
Absorption peaks caused by stretching vibration are usually the most intense
peaks in the IR spectrum. If the bond strength increase and the masses of the atom
decrease, the value of vibrational frequency increases. On the basis of Hooks law. We
can predict that O-H bond requires more energy for stretching vibration than C-C bond.
Hence in IR spectrum O-H stretching bond will appear in higher wave number region
9high energy region 3600cm-1) and C-C stretching bond will appear in lower number
region(low energy region 1200cm-1).
Calculation of reduced mass
1. For O-H stretching vibration

µ = m1m2
m1+m2

µ = 16x1
16+1

µ = 16
17
µ = 0.9411

2. For C-C stretching vibration

µ = m1m2
m1+m2

Page 24 of 38
 µ = 12x12
16+12

µ = 144
24
µ= 6

Fundamental modes of vibration

The fundamental modes of vibrations are determined by stretching and bending
modes. At certain quantized frequencies stretching and bending vibrations of a bond can
occur. Radiations are absorbed at a particular vibaration only if it causes change in the
dipole moment of the molecule. The vibrational frequency of a bond increases with
increases in bond strength. There is very important requirement for a molecule to show
and infra read spectrum its states that dipole moment of the molecule must change during
the vibration. Homonuclear diatomic molecules such as H2O2, N2 etc are IR inactive
where as hetronuclear diatomic molecule such as CO, NO, CN, HCl are IR active
The number of fundamental modes of vibration for a molecule can be calculated
from the total number of atoms present in the molecule. The molecule containing 'n'
number of atoms will have '3n' degrees of freedom. The fundamental modes of vibration
are depends on the geometry of molecule and can be calculated as follows:
1) For linear molecule:
There are only two degrees of rotation. It is due to the fact that the
rotation of such a molecule about its axis of linearity does not bring about any
change in the position of the atoms while rotation about the other two axes
changes the position of the atoms. Thus, for a linear molecule containing n
atoms,
Total degrees of freedom =3n
Translational degrees of freedom =3
Rotational degrees of freedom =2
Hence, Vibrational degrees of freedom = 3n-(3+2)
= 3n-5
Hence for linear molecule, containing n atoms, there are (3n-5)
possible fundamental modes of vibrations.
e.g.
Nitrous oxide (NO)
Total atoms (n) =2
Applicable formula (3n-5)
Fundamental modes of vibration = 3x2-5
= 6-5
=1
2) For non-linear molecule:

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 There are three degrees of rotation as the rotation about all the three axes
(X, Y, and Z) will result in a change in the position of the atoms. Thus, for a non-
linear molecule containing n atoms,
Total degrees of freedom = 3n
Translational degrees of freedom =3
Rotational degrees of freedom =3
Hence, Vibrational degrees of freedom = 3n-(3+3)
= 3n-6
Hence for linear molecule, containing n atoms, there are 3n-6 possible
fundamental modes of vibrations.
e.g.
Methane Molecule (CH4)
Total atoms (n) =5
Applicable formula (3n-6)
Fundamental modes of vibration = 3x5-6
= 15-6
=9

Following table no. 1.

Shows fundamental modes of vibrations for different molecules.
Sr. Molecule Total no. of Geometry of Applicable Fundamental
No. atoms (n) the molecule formula modes of
vibration
1 NO 2 Linear 3n-5 1

2 CO2 3 Linear 3n-5 4

3 C2H2 4 Linear 3n-5 7

3 H2O 3 Non-linear 3n-6 3

4 NH3 4 Non-linear 3n-6 6

5 CH4 5 Non-linear 3n-6 9

6 C6H6 12 Non-linear 3n-6 30

Spectral range
IR region 2.5 to 15 um (4000cm"1 to 667 cm"1) is subdivided into three sub regions,
a. Functional group region 2.5 to 7.7 μm (4000-1300 cm-1)
b. Finger print region 7.7 to 11 μrn (1300 to 909 cm-1)
c. Aromatic region 11 to 15μm (909-667 cm-1)

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 a. Functional group region:
This region is very useful for organic chemists. Bands due to stretching
vibrations of functional groups such as O-H, N-H, C-H, S-H in the range 2500- 3700 cm-1
are shown in this part of IR spectrum.
The absorption band at 2100-2500 cm'1 shows the presence of CN, CH=CH bond
and is known as triple bond region. The IR absorption band at 1500-1600 cm-1 indicates
the presence of aromatic C=C stretching frequency, similarly at 1620 - 1680 cm-1 is due
to alkenes, C=C stretching frequency. The important IR absorption band at 1700 cm-1,
clearly indicates the presence of carbonyl group (C=O) may be aldehydes or ketone. Thus
functional groups in the molecule can be identified from absorption bands in IR.
a. Finger print region:
The region between 7.7-11 μrn (1300 to 909 cm-1) is known as finger print
region because the pattern of absorptions in this region are unique to any particular
compound, just as a person's fingerprints are unique. This is the most complex part of IR
spectrum and contains number of absorption bands. These absorption bands appear due to
stretching and bending vibrations. This region is not of much useful because of its
complexity but helpful for a sample comparison. Some molecules containing the same
functional group show similar absorptions above 1500 cm-1 but their spectra differ in
finger print region If the finger print region of two samples are identical, then these
samples are also identical.
b. Aromatic region:
The region between 11-15μm (909-667 cm-1) is known as aromatic region. This
part helps to detects aromaticity of the compound. The lack of absorption in this region
shows presence of non-aromatic compound. The bands occur in this region is due to
bending vibrations. This region also useful in determination of substitution patterns on
aromatic compounds such as ortho, meta, para substitution. Though most of the covalent
bonds have characteristic and invariable wavelength of absorption, but sometime due to
environmental conditions like conjugation, hydrogen bonding, electron donating or
withdrawing group, IR spectra are slightly shifted. The exact position of absorption
depends on force constant, masses of the atoms, environment of the bond. The table
shows characteristic IR absorption frequencies of some functional groups

Page 27 of 38
 Table No. 2. Infrared absorption of some functional groups
Frequency range (cm-1) Bond Type of Compound

[A] Bonds to Hydrogen atom:

3600-3650 -O-H (free) Alcohols, Phenols

3200-3500 -O-H(bonded) Hydrogen bonded alcohol & phenol

3450-3600 sharp Inter molecular 'H' bond

3200-3550 broad Intra molecular 'H' bond

2500-3200 Very broad Cheleted 'H' bond

3300-3350 -N-H Amines, Amides

3200-3310 =C-H Acetylenic

3000-3100 =C-H Ethylenic & aromatic

2850-2950 -C-H Saturated alkanes

2700-2900 -CHO Aldehydes

2550-2900 -S-H Thiols

2500-3600 -COOH Carboxylic acids (very broad)

[B] Triple Bond Region:

2240-2260 -ON Nitriles (Non conjugated)

2215-2240 -C=N Nitriles (Conjugated)

2100-2140 -OC-H Terminal alkynes

2200-2260 -OC-H Non terminal alkynes

[C] Double Bond Region:

O O

1740-1850 Anhydrides
R O R

Page 28 of 38
 O

1770-1815 Acid halides

R X
O

1730-1750 Esters
R
R O
O
1730-1740 Aldehydes

R H
O
1705-1720 Ketones
R R
O

1700-1725 Acids (Carboxylic)

R OH
O

1680-1700 Amides
R NH2

HC CH
1620-1680 Alkenes

1590-1690 -C=N- Imines, Oximes

1500-1600 Aromatic
C C

1370-1540 -NO2 Nitro group

[D] Single Bond Region

1000-1300 Alcohol, Phenol, Ester, Ether etc.

C O

1100-1120 C C Saturated alkanes

500-750 C X Halo-alkanes

[E] Aromatic Region (=C-H Bending)

Page 29 of 38
690-710
730-770 CH Mono-substituted benzene

735-770
CH(O) Ortho-substituted benzene

750-810 CH(m) Meta-substituted benzene

790-850 CH(p) Para-substituted benzene

Structure of Organic Compounds

1. Structure of H2O molecule
Total atoms (n) =3
Applicable formula (3n-6)
Fundamental modes of vibration = 3x3-6
= 9-6
=3
There for water is a triatomic nonlinear molecule. In this molecule two stretching
frequency such as 3650cm-1, 3760cm-1 and one bending vibration appears at 1600cm-1.
All the three vibrations gives change in dipole moment and hence water molecule are IR
inactive
2. Structure of CO2 molecule
Total atoms (n) =3
Applicable formula (3n-5)
Fundamental modes of vibration = 3x3-5
= 9-5
=4
The symmetrical stretching mode produces no change in the dipole moment of
the molecule and therefore it is IR inactive.

In the asymmetrical stretching mode, the two C=O bonds stretch out of phase;
one C=O bond stretches as the other contracts. The asymmetrical stretching mode, since
it produces a change in the dipole moment, is IR active; the absorption (2350 cm"1) is at a
higher frequency (shorter wavelength) than observed for a carbonyl group in aliphatic
ketones. This difference in carbonyl absorption frequencies displayed by the carbon

Page 30 of 38
dioxide molecule results from strong mechanical coupling or interaction. In contrast, two
ketonic carbonyl groups separated by one or more carbon atoms show normal carbonyl
absorption near 1715 cm"1 because appreciable coupling is prevented by the intervening
carbon atom(s). The bending vibrations in 3 and 4 above are equivalent and there
frequencies must be identical because turning the plane of vibrations cannot alter the
frequencies.
3. Structure of Acetone molecule
Acetone is a saturated aliphatic ketones i.e. acetone shows a strong C=O
(carbonyl) stretching absorption band at 1715cm-1.

It's relatively constant position, high intensity and relatively freedom from
interfering bands makes this one of the easiest band to recognize in IR spectra. Changes
in the environment of the carbonyl can either lower or raise the absorption frequency
from this normal value. The absorption frequency observed for a neat sample is increased
when absorption is observed in nonpolar solvents. Polar solvents reduce the frequency of
absorption. The overall range of solvent effects does not exceed 25 cm-1. The band at
3000 cm-1 suggests a methyl stretching vibration whereas the bands at 1370 and 1430 cm-
1
can be assigned to symmetrical and asymmetrical methyl bending vibrations. The
presence of the combination band for C-C-C near 1218 cm-1 further confirmed the
presence of carbonyl group in acetone.
4. Structure of Alkane(Ethane) molecule
Ethane gives two absorption strong absorption bands in high frequency region.
One band at 2940cm-1 due to-C-H asymmetric stretching and another band at 2880cm-1
due to symmetric stretching vibration. Asymmetric C-H bending vibration appears at
1465cm-1 while symmetric C-H bending vibration appears at 1380cm-1

5. Structure of 1-propanol molecule

Page 31 of 38
 IR spectra of 1-propanol give two characteristic O-H and C-O stretching
bands. These vibrations are sensitive to hydrogen bonding due to O-H group of
alcohol gives a sharp band at 3610cm-1. A strong broad band appears in3600cm-1
region due to O-H stretching involved in hydrogen bonding. Primary alcohol show
characteristic strong broad band at 1050cm-1.

6. Structure of Benzene molecule

IR spectrum of Benzene molecule gives C-H stretching band accurs in
3100cm-1, 3000cm-1 region. Absorption bands due to C-C stretching accurs at
1600cm-1, 1580cm-1, 1500cm-1 and 1450cm-1. In plane C-H bending absorption
bands appear in 1300cm-1-1000cm-1 region and out of plane C-H bending
absorption bands appear in 900cm-1-675cm-1 region.

7. Structure of Benzmide molecule

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 IR spectrum of benzmide molecule gives
N-H stretching - 3370cm-1due to asymmetric stretching
N-H stretching -3170cm-1 due to symmetric stretching
C=O -1660cm-1 doe to conjugation with one
pair of electron on nitrogen atom
N-H -1631cm-1 bending in amide group

G. PURIFICATION OF ORGANIC COMPOUNDS

1) Sublimation
Purification of solid organic compounds is done by the sublimation. Its used for
those compounds which on heatng pass readily and directly from solid to vapour state,
with a sbsquint ready reversal of this process when the vapour is cooled in a small
evaporating basin the dry crude material is placed which is then kept on a wire gauze. It
is then covered with a filter paper which is pierced by a number of small holes made in
an upward direction. A glass funnel is then inverted over the paper as shown in the figure.
The basin is then gently heated by a small Bunsen flame, which should be carefully
protected from side draughts by screens, so that the material in basin receives a steady
uniform supply of heat. The material vaporizes and the vapor passes up through the holes
into the cold funnel. Here it cools and condenses as fine crystals on the upper surface of
the paper and on the walls of glass funnel. Heating is stopped when almost the whole of
the material in evaporating basin has vaporized, and then the pure sublimed material
collected. In using such an apparatus, it is clearly necessary to adjust the supply of heat so
that the crude material in basin is being steadily vaporized, while the funnel does not
became more than luke-warm.-Cotton

Page 33 of 38
 Fig. 3.20 Sublimation
2) Crystallization or Recrystalllization:-
The important and delicate method in which the purification of solid organic
compounds takes place is the crystallization process. It consists of dissolving the
substance in minimum amount of a solvent in which the substance is more soluble in hot
than in cold. By filter in with hot solution the impurities are removed then the filtrate is
allowed to cool when crystals of pure substance are obtained. These are filtered ad if
necessary, again dissolved for crystallization. It should be noted that on cooling of the
filtrate yields tiny but purer crystals whereas on slow cooling yields bigger but impure
crystals. Mother liquor is the liquid left after separation of crystallized product. It is
concentrated by evaporation and cooled to obtain a fresh crop of crystals of pure
substance which are further subjected to crystallization. Maximum amount of pure
substance is recovered by repeating the process several times. The following suggestions
are helpful in increasing the efficiency of crystallization.

Fig. 3.20 Crystallization

a) Selection of suitable solvent: The suitable solvent is selected which is of great

importance in purification of substance by crystallization. The solvent is selected on the
'hit and trial' basis and it is necessary to try a number of solvents before arriving at a
conclusion. If the solvent dissolves the substance in cold or large excess of hot solvent is
require to dissolve the substance it is obviously unsuitable for crystallization. Only that
solvent is to be selected which does not dissolve or dissolves a very small amount of
substance in cold but dissolves its appreciable amount on boiling or heating. If none of
the solvent appears good enough for crystallization, a combination of two or more

Page 34 of 38
solvents may be employed. Solubility of nonpolar substances is generally in nonpolar
solvents, where as solubility of polar substances is in polar solvents. Some of the
common solvents in order of increasing polarity are: petroleum ether, carbon
tetrachloride, benzene, chloroform, diethyl ether, acetone, ethyl acetate, ethyl alcohol and
water.
b) Drying of crystallized substance: the safe and reliable method for drying, through
much time consuming, is the use of desiccators with vacuum arrangement known as
vacuum desiccators. On a watch glass the crystallized substance is spread over and kept
in the vacuum desiccators and vacuum is applied. The substance is allowed to stay under
these conditions for several hours and then the vacuum is released very slowly when the
dry crystallized substance is obtained.
c) Decolourisation of undesirable colours: The impurity of colouring matters is
removed by boiling the substance in solution with a sufficient quantity of finely
powdered animal charcoal for about 15 to 30 minutes and then filtering the hot solution.
The animal charcoal adsorbed the coloured impurities and the pure decolorized substance
crystallizes out from the filtrate on cooling. As the animal charcoal is insoluble in all the
common solvents it can be employed in the solvent used for crystallization.
3) Paper Chromatography
It was the invention of Cambridge school of workers, A.J.P. Martin and his
coworkers. Mixture of organic substances such as dyes and amino acids was separated by
the use of this technique. Now a day cations and anions of inorganic substances can also
be seprated by the use of this technique.

Principal
In this type of chromatography the substances is distributed between two phases.
i. Stationary phase
ii. Moving phase
On the paper components of the mixture are separated and they migrate at
different rates and appear as spots at different points.
Working
In this technique, a drop of test solution is applied as a small spot on a filter paper
and the spot is dried. In a closed chamber paper is kept and the edge of the filter paper is
dipped into a solvent called developing solvent. As soon as the filter paper gets the liquid
through its capillary axis and when it reaches the spot of the test solution (a mixture of
two or more substances), the various substances are moved by solvent system at various
speeds. When the solvent has moved these cations to a suitable height (15 - 18 cm) the

Page 35 of 38
paper is dried and the various spots are visualized by suitable reagents called visualizing
reagents. The Rf values that is migration parameters gives the movement of substances
relative to the solvent.
Migration parameters
On the chromatograms the position of migrated spots is indicated by a term
called as RF. RF: The R is related to the migration of the solute front relative to the
solvent. Distance travelled by the solute from the origin line. Distance travelled by the
solvent from the origin line.
The RF value of substance depends on the following factors:
The nature of the compound
The size of the vessel in which the operation is carried out
The temperature
The solvent employed
The medium used for separation, i.e., the quality of paper.

Fig. 3.21 paper Chromatography

Questions:-
1. Discuss briefly the principal of IR spectroscopy.
2. Write note on fundamental vibration of nonlinear molecule.
3. Write a short note on finger print region.
4. Define Electronic spectroscopy. What is its absorption range?
5. Calculate the energy associated with the radiations having wave number 3 x 10
per cm.
6. Write a short note on Electromagnetic spectrum.
7. Define the following terms:
i) Bathochromic shift ii) Hypsochromic shift iii) A Chromophore
iv) Hyperchromic
8. Define the term chromophore. How will you detect the presence of carbonyl
group in aldehydes and ketones?
9. Discuss the various types of electronic transitions and explain the effect of the
polarity of the solvent on the each type of transition.
10. "A conjugated diene absorbs at a higher wavelength with with higher value of
extinction coefficient as compare to a diene in which double bonds are isolated."
Comment on this statement with examples giving the chemistry involved.

Page 36 of 38
11. What types of transitions are observed in a, p-unsaturated carbonyl compounds?
How absorption maximum and intensity are shifted when carbonyl group is not
conjugated? Discuss the effect of solvent polarity on R-band.
12. Aniline absorbs at 280 nm (ξmax 8600), however in acidic solution, the main
absorption band is seen at 203 nm. Explain.
10. The position of absorption of acetone shift in different solvent 279 nm (hexane),
272 nm (ethanol), and 264.5 nm (water).explain.
11. (a) The UV spectrum of acetone shows two peaks at
λmax = 280 nm ξ max 15and λmax = 1900 nm ξ max 100
i) Identify the electronic transition for each
ii) Which one of these is more intense?
(b) Why is methanol a good solvent for UV but not for IR determination?
12. "Increase in polarity of the solvent shift π → π *band to longer wavelength but
n→ π *and n - σ* bands to shorter wavelength". Comment on the statement.
13. a) Write notes on K band, B band and R band.
b) Which solvents are generally used, in UV spectroscopy and why.
14. Identify the types of transitions in each of the following compounds
i) Ethanol =290nm ξ max 17
ii) Acetic anhydride = 227 nm ξ max 44
iii) Pentadiene l, 3 = 224nm ξ max 22650
iv) Crotonaldehyde = 214 nm ξ max 15850
v) Styrene = 282 nm ξ max 450
15. What type of transitions will be expected to occur in each of the following?
i) CH3CHO ii) (CH3)2NCH=CH2
16. What are different types of vibrations? How fundamental modes of vibrations are
calculated for linear and non linear molecules.
17. Calculate fundamental modes of vibrations for the following molecules:
Benzene, Hydrogen peroxide, Carbon disulphide, Ammonia, Water, and
Methane.
18. What are essential requirements for a substance to absorb in the IR region?
19. How will you distinguish between the following pairs of compounds by using IR
spectroscopy?
a) Ethanol & Diethyl ether
b) m-cresol & anisole
c) Acetone & Acetic acid
20. Explain the following:
a) Acetaldehyde absorbs at 1725 cm-1, acetone absorbs at 1715 cm-1
While benzaldehyde absorbs at 1710 cm-1.
b) Benzaldehyde absorbs at 1710 cm-1 while salicyladehyde absorbs at
1698 cm-1.
21. An organic compound C8H8O shows absorption frequencies at 1680, 1600, 1500,
1430, 1360, 690 cm-1. Assign the structure.
22. Explain the following
a) Sublimation
b) Crystallization

Page 37 of 38
c) Paper chromatography.

Page 38 of 38