SPECTROSCOPY – MODULE 11

INTRODUCTION
Spectroscopy is one of the most powerful tools available for the study of atomic and
molecular structure, and is used in the analysis of most of the samples.

Spectroscopy deals with the study of interaction of electromagnetic radiation with the
matter. During the interaction, the energy is absorbed or emitted by the matter. The
measurement of this radiation frequency (absorbed or emitted) is made using spectroscopy.

TYPES OF SPECTRA
Based on the nature of interaction of electromagnetic radiation, spectra can be
classified into two types.

1. Absorption spectrum: - When an atom or molecule undergo a transition from the lower
energy level, E1 to the higher energy level E2 with an absorption of a photon of energy hⱱ, the
spectrum obtained is called an absorption spectrum. Important absorption spectra are UV-
Visible, IR, Microwave and NMR spectrum.

2. Emission spectrum: - When an atom or molecule undergo a transition from the higher
energy level, E2 to the lower energy level E1 with an emission of a photon of energy hⱱ, the
spectrum obtained is called an emission spectrum. Hydrogen spectrum, atomic emission
spectrum etc.

Based on the nature of interacting species, spectra can be classified into two types.

1. Atomic spectroscopy

It deals with the interaction of the electromagnetic radiation with atoms.

During which the atoms absorb radiation and gets excited from the ground state electronic
energy level to another.

2. Molecular spectroscopy

It deals with the interaction of electromagnetic radiation with molecules. This results in
transition between rotational, vibrational and electronic energy levels. UV-Visible, IR,
Microwave and NMR spectra are belonging to this category.

1
Differences between molecular spectra and atomic spectra

Sl.No. Atomic Spectra Molecular Spectra

It occurs from the interaction of

It occurs from the interaction of
1 molecules + electromagnetic
atom + electromagnetic radiation
radiation
Molecular spectra is a
2 Atomic spectra is a line spectra
complicated spectra
It is due to vibrational, rotational
It is due to electronic transition in
3 and electronic transition in a
an element
molecule.
BEER LAMBERTS LAW
According to this law, "when a beam of monochromatic radiation is passed through a
solution of an absorbing substance, the rate of decrease of intensity of radiation 'dl with
thickness of the absorbing solution 'dx' is proportional to the intensity of incident radiation ‘I’
as well as the concentration of the solution 'C'.

It is mathematically represented as

Where, log absorbance (or) Optical density.

= Molar absorptivity coefficient.

The equation is called Beer-Lambert’s law. Thus, the absorbance (A) is directly
proportional to molar concentration (C) and thickness (or) path length (x)

log absorbance (or) Optical density.

T = It / I0

T % = It / I0 x 100

A = log 1/ T

Problem 1: - Find out the absorbance (or) optical density of a solution, if the
transmittance of a solution is 18.5%.
2
Solution

Given: Percentage of transmittance (%T) = 18.5% (or) Transmittance (T) = 0.185.

Absorbance (or) optical density,

Absorbance = 0.733

Problem 2:- The percentage transmittance of 5 x 10-4 M solution of disodium fumarate

in a 1 cm cell is 19.2%. Calculate (i) the absorbance (A), (ii) the molar absorption
coefficient .

Solution

Given: % T= 19.2% (or) T=0.192; C = 5 ×10-4M

(i) Absorbance, A = -log T = - log 0.192 = 0.717

(ii) The molar absorption coefficient

= 1.434×103 mol dm-3cm-1

Problem 3: - A solution shows a transmittance of 20% when taken in a cell of 2.5 cm

thickness. Calculate its concentration if the molar absorption coefficient is 12,000 dm3
mol-1 cm-1.

Solution

Given: %T = 20%; T= 0.20; x = 2.5; = 12,000 dm3 mol-1 cm-1

A = - log T = –log 0.20 = 0.699

We know that, A = Cx

Problem 4: - Calculate the molar absorption of a solution 1×10-4 M. The

absorbance of which is 0.20, when the path length is 2.5 cm.

Solution

Given: A=0.20; C=1×10-4; x = 2.5cm

3
 We know that, A =

Molar absorption = 800 dm3 mol–1 cm–1

Problem 5: - A monochromatic radiation is incident on a solution of 0.05 M

concentration of an absorbing substance. The intensity of the radiation is reduced to
one-fourth of the initial value after passing through 10 cm length of the solution.
Calculate the molar extinction co-efficient of the substance.

Solution

According to Beer-Lambert law, log

Given: C = 0.05 M; x = 10 cm; l = 1/4; l0 = 1; =? The above equation may be

written as

Molar extinction co-efficient = 1.204 dm3 mol–1 cm–1

Problem 6

A-solution of thickness 2cm transmits 40% incident light. Calculate the concentration
of the solution, given that = 6000 dm3 mol–1 cm–1

Solution

Given: % T = 40%; T = 0.40; x = 2.0 cm; = 6000 dm3 mol–1 cm–1

A = –logT = –log 0.40 = 0.3980

We know that,

Concentration = 3.316 x 10–5mol dm- 3.

Problem 7: - At definite wave length, an absorber when placed in a cell of 1 cm path length
absorbs 20% of the incident light. If the absorptivity of the absorber at this wave length is 2.0,
find out its concentration.

Solution

Given: l = 100 –20 = 80; l0 = 100; = 2; x = 1

4
 According to Beer-Lambert's law, log

= log 1.25 = 2C = 0.0969 - 2C

C = 0.0969. + 2

Concentration = 0.048 g/lit

Problem 8: - A solution of thickness 2 cm transmits 40% incident light. Calculate the

concentration of the solution, given that

= 5842 dm3 mol-1 cm–1

Given: %T = 40%; T= 0.40; x = 2 cm = 5842 dm3 mol-1 cm- 1

A = –log T– log0.40 = 0.398

We know that, A = Cx

UV-V1SIBLE SPECTROSCOPY
Principle

Ultraviolet (UV) Visible-spectra arises from the transition of valence electrons within
a molecule or ion from a lower electronic energy level (ground state E 0) to higher electronic
energy level (excited state E l). This transition-occurs due to the absorption of UV
(wavelength 100–400 nm) or visible (wavelength 400–750 nm) region of the electronic
spectrum by a molecule (or) ion. The actual amount of energy required depends on the
difference in energy between the ground state and the excited state of the electrons.

Chromophores & Auxochromes

Electronic transition depends on the electronic structure of the absorbing medium

(sample). The absorption of UV -visible radiation in organic molecule, is mainly due to
presence of certain functional groups.

The two important groups, responsible for absorption and position of absorption in
UV -visible spectra are

5
 1. Chromophores

2. Auxochromes

1. Chromophores

The presence of one or more unsaturated linkages (π-electrons) in a compound is

responsible for the colour of the compound, these linkages are referred to as chromophores.

The part of the molecule containing the electrons involved in the electronic
transition which give rise to an absorption is called Chromophore

Examples

Two types of Chromophores are

1. Chromophores which contain π electrons can undergo π→π* transitions. Eg; ethylene,
acetylene etc

2. Chromophores which contain both π and n electrons can undergo π→π*and n→π*
transitions.eg; carbonyls, nitriles etc

2. Auxochrome

It refers to an atom or a group of atoms which does not give rise to absorption band on
its own, but when conjugate to chromophore will cause a shift. These are the colour
enhancing groups

An Auxochrome is a functional group of atoms attached to the chromophore

which modifies the ability of the chromophore to absorb light, altering the wavelength
or intensity of the absorption.

Examples; - OH, - NH2, - CI, - Br, -1, etc.

Some important definitions related to change in wavelength and intensity

1 Shift to higher wave length (lower

Bathochromic shift, (red shift)
1. frequencies).

2 Shift to lower wavelength (higher

Hypsochromic shift. (blue shift)
2. frequencies).
3
Hyperchromic effect. An increase in intensity.
3.
4
Hypochromic effect. A decrease in intensity. '
4.

Illustration

6
 In chloroethylene, CH2 = CHCl,

C = C is a chromophore. CI is an auxochrome.

Substitution of a hydrogen atom in ethylene by a halogen atom causes a hypochromic

shift and a hyperchromic effect.

Difference between Chromophore and auxochrome

SI.No Chromophore Auxochrome

It does not impact colour, but

This group is responsible for the
1 when conjugate to chromophore
colour of the compound.
produce colour.

2 It does not form salt But it forms salt

3. It contains at least multiple bond It contains lone pair of electrons

Example: Example:

–NO2, –NO,–N=N– –OH

Types of electrons involved in organic molecule

The energy absorbed by an organic molecule involves transition of valence electrons.
The following three types of electrons are involved in the transition.

Energy required
SI.No Electrons Examples to excite Present in
electrons

Saturated long chain hydrocarbons.

Higher than UV
1 electrons (Paraffins) (CH3-CH2-CH2-CH3) Single Bond
light

Double bond and

Unsaturated hydrocarbons like
UV (or) visible triple bonds.
2 π electrons dienes and trienes and aromatic
light
compounds. (unsaturated
bond)

Organic compounds containing N,O Unshared (or) non

3. n- electrons (or) halogens
UV radiation
bonded electrons.

Thus, the unsaturated hydrocarbons and compound containing N, O, S may

absorb visible (or) UV radiations.

Example

The three types of electrons are shown in the molecule; (HCHO).

7
Types of transitions involved in organic molecules
Energy absorbed in the visible and UV region by a molecule causes transitions of
valence electrons in the molecule. These transitions are

The energy level diagram for a molecule is shown in the fig 1.1. The energy values
for different transitions are in the following order.

1. Transitions
  * Transitions occur in the compounds, in which all the electrons are involved in
single bonds and there are no lone pair of electrons.

The energy required for transition is very large. -The absorption band occurs
in the far UV region' (120-136 nm).

Example: - Saturated hydrocarbons (CH4, CH3 - CH3, CH3 - CH2 - CH3, etc.,)

CH 4 : For   * ;  max  121.9nm

(i)
■■■,

(ii)

8
 2. Transitions

n  * Transitions occur in the saturated compounds containing lone pair (non-

bonding) of electrons in addition to transitions. The energy required for an
transition is less than that required for a transition. This absorption band
occurs at longer wave length in the near UV region (180-200 nrn).

Example:-

3. Transitions
Transitions occur due to the transition of an electron from a bonding π orbital
to an antibonding π* orbital. These transitions can occur in any molecule having a π electron
system. Selection rule determines whether transitions to a particular π *orbital is allowed or
forbidden.

4. Transitions
n —> π* transitions are shown by unsaturated molecule containing hetero atoms like N,
O & S. It occurs due to the transition of non-bonding lone pair of electrons to the antibonding
orbitals. This transition shows a weak band, and occurs in longer wavelength with low
intensity.

Examples: - (i) Aldehyde & ketone having no

)

n —> π * transition occurs in the range of 270-300 nm.

(ii) Aldehyde & ketone ( (having double bond).

n →π* transition occurs in the range of 300-350 nm.

Example

1. UV spectrum of ethylene

It shows intense band at 174 nm and weak band at 200 nm. Both are due to
transitions. According to selection rules, the intense band at 174 nm is due to allowed
transition.

Alkyl substitution of the olefins moves the absorption to a longer wavelength. This is
known as bathochromic effect or red shift. This effect increases with increase of alkyl group.

2. UV-spectrum of unsaturated ketone

9
 It shows that the low intensity band at 324 nm is due to transition, and high
intensity band at 219 is due to transition.

Instrumentation of UV-Vis spectrophotometer

A spectrophotometer is a device which detects the percentage transmittance of light
radiation when light of certain intensity and frequency range is passed through the sample.
Thus the instrument compares the intensity of transmitted light with that of incident light.

Components: - The various components of a visible UV spectrometer are as follows.

1. Radiation source

In visible - UV spectrometers, the most commonly used radiation sources are

hydrogen (or) deuterium lamps.

Requirements of a radiation source

(a) It must be stable and supply continuous radiation.

(b) It must be of sufficient intensity.

2 Monochromators

The monochromator is used to disperse the radiation according to the wavelength.

The essential elements of a monochromator are an entrance slit, a dispersing element an exit
slit. The dispersing element may be a prism or grating (or) a filter.

3. Cells (sample cell and reference cell)

The cells, containing samples or reference for analyzing should fulfill the following
conditions.

(i) They must be uniform in construction.

(ii) The material of construction should be solvents.

(iii) They must transmit the light of the wavelength used.

4. Detectors

There are three common types of detectors used in UV visible spectrophotometers.

They are Barrier layer cell, Photomultiplier tube and Photocell.

The detector converts the radiation, falling on which, into current. The current is
directly proportional to the concentration of the solution.

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5. Recording system

The signal from the detector is finally received by the recording system. The
recording is done by recorder pen.

II Working of UV and visible spectrophotometer

The radiation from the source is allowed to pass through the monochromator unit. The
monochromator unit allows a narrow range of wavelength to pass through an exit slit. The
beam of radiation coming out of the monochromator is split into two equal beams. One-half
of the beams (the sample beam) are directed to pass through a transparent cell containing a
solution of the compound to be analyzed. The half (the reference beam) is directed to
pass through an identical cell that contains only the solvent. The instrument is designed in
such a way that it can compare the intensities of the two beams. If the compound absorbs light
at a particular wavelength, then intensity of the sample beam (I) will be less than that of the
reference beam (l0). The instrument gives output graph, which is a plot of wavelength Vs
absorbance of the light. This graph is known as an absorption spectrum.

Block diagram of UV-visible spectrophotometer

Applications

1. Detection of functional group

UV spectroscopy of an organic compound gives information about functional group

containing π bond and non-bonding electrons.

2. Qualitative analysis

UV absorption spectroscopy is used for characterizing and identification of aromatic

compounds and conjugated olefins by comparing the UV absorption spectrum of the sample
with the same of known compounds available in reference books.

3. Detection of impurities

UV absorption spectroscopy is the best method for detecting impurities in organic

compounds, because the bands due to impurities are very intense.

4. Quantitative analysis

Determination of substances: UV absorption spectroscopy is used for the

quantitative determination of compounds, which absorbs UV. This determination is based on
Beer's law

11
where, = molar extinction coefficient (constant), C = concentration ,x = length of the cell

First, absorbance (optical densities) of the different solutions of known concentrations

is measured. Then the graph is plotted between absorbance vs concentration (calibration
curve). A straight line is obtained. Then absorbance of unknown solution is measured. From
the graph the concentration of unknown substance is found out.

5. Determination of molecular weight

Molecular weight of a compound can be determined if it can be converted into a

suitable derivative, which gives an absorption band.

6. Studying kinetics of chemical reactions

Kinetics of chemical reactions can be studied using UV spectroscopy by following the

change in concentration of a product or a reactant with time during the reaction.

INFRARED SPECTROSCOPY
IR spectroscopy deals with the infrared region of the electromagnetic spectrum. The
range in the electromagnetic spectrum extending from 12500 to 50 cm - 1 is commonly
referred to as the infrared (IR). This region is further divided into three sub regions.

1. Near infrared: - This region is from 12500 to 4000 cm–1

2. Infrared (or) ordinary IR: - This region is from 4000 to 667 cm–1

3. Far infrared: - This region is from 667 to 50 cm–1

The vibrational spectral (IR spectra) region at 1400 - 700 cm–1 gives very rich and
intense absorption bands. This region is termed as finger print region. Finger print region
can be used to detect the presence of functional group and also to identify and characterize
the molecule just as a finger print can be used to identify a person. The region 4000 - 1430
cm- l is known as Group frequency region.

Principle

IR spectra are produced by the absorption of energy by a molecule in the infrared

region and the transitions occur between vibrational energy levels of a molecule, having
change in dipole moment with vibration of a bond. So, IR spectroscopy is also known as
vibrational spectroscopy.

In IR spectroscopy an organic molecule is exposed to IR radiation. When the radiant

energy matches the energy of a specific molecular vibration, absorption occurs and peak is
observed.

12
 Different functional groups absorb characteristic frequencies of IR radiation, hence
gives particular peak value. In IR spectrum wave number is plotted on the x- axis and
percentage transmittance is plotted on the y-axis.

Criteria for a compound to be IR active

When energy in the form of IR radiation is applied, it causes vibration of atom in a molecule
if;

i) Correct wavelength of radiation: - frequency of incident radiation must exactly

corresponds to the frequency of particular vibration mode

ii) Change in dipole moment (charge x distance): - The dipole moment of the molecule
must vary during vibration so that interaction with radiation is possible.

For eg. When a hetero nuclear diatomic molecule like HCl undergo stretching vibration the
dipole moment changes with change in inter nuclear distance and shows IR
activity. Whereas homo nuclear diatomic molecules like H 2, O2, N2 etc. are not
vibrationally active as they possess no change in dipole moment with stretching
vibration.

Molecular Vibrations
Since atoms in a molecule are continuously vibrating, molecules are also vibrating.
There are two kinds of fundamental vibrations in the molecule.

1. Stretching vibrations

During stretching the distance between two atoms decreases or increases, but bond
angle remains unaltered.

Types of stretching vibrations

(a) Symmetric stretching: - In this type the movement of the atoms with respect to a
particular atom in a molecule is in the same direction. As a result of symmetric
stretching in a molecule bond length increases or decreases.

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 (b) Asymmetric stretching vibrations: - In these vibrations, one atom approaches the
central atom while the other departs from it. As a result of asymmetric stretching
bond length changes.

2. Bending (or) deformation vibrations

During bending bond angle increases and decreases but bond distance remains
unaltered.

Vibrational changes depend on the masses of the atoms and their spatial arrangement
in the molecule. When IR light of the same frequency is incident on the molecule, energy is
absorbed resulting in increase of amplitude of vibration. When the molecule returns from the
excited state to the original ground state, the absorbed energy is released as heat.

Thus, every compound shows characteristic absorption bands in the IR region of the
spectrum. Different functional groups produce easily recognizable band at definite positions
in the IR spectral range (12500 to 50 cm–1)

Types of bending vibrations

(a) Scissoring: - In this type, the atoms move away and come close to each other in
the same plane just like blades of scissor.

(b) Rocking: - In this type, the movement of atoms take place in the same direction.

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

(d) Wagging; - In this type, two atoms move up and below the plane with respect to
the central atom.

Number of stretching and bending vibrations

14
 The number of fundamental (or) normal vibrational modes of a molecule can be
calculated as follows.

For Non-linear molecule

A non-linear molecule containing ‘n’ atoms has (3n - 6) fundamental vibrational

modes.

Example

(i) CH4 → (3 ×5 - 6) = 9 fundamental vibrational modes.

ii) H2O → (3 ×3 - 6) = 3 Fundamental vibrational modes

2. For linear molecules

A linear molecule containing ‘n’ atoms has (3n-5) fundamental vibrational modes.

Example: - CO2 → (3×3–4) = 4 fundamental vibrational modes.

Illustrations
1. Water (n = 3)

Water is a bent (non-linear) triatomic molecule, and has 3n–6 = (3×3–6) =3

fundamental vibrational modes. They are symmetric stretching, asymmetric stretching and a
bending mode. These modes and their corresponding frequencies are shown below

In general stretching frequencies are much higher than bending frequencies. This is
because; more energy is required to stretch a bond than to bend it. All the above 3 vibrations
are said to be active (change in dipole moment during the vibration) in the IR region and the
IR spectrum of water exhibits 3 absorption bands at 1596, 3652 and 3756 cm –1 corresponding
to the bending, symmetric stretching and the asymmetric stretching vibrations respectively.

Thus, for a vibration to be active in IR, the dipole moment of the molecule must
change.

2. Carbon dioxide (n = 3)

15
 Carbon dioxide is a linear triatomic molecule, and has 3n- 5 = (3 x 3 - 5) = 4
fundamental vibrational modes. Symmetric stretching, asymmetric stretching and two
bending vibrations in two mutually perpendicular planes. These modes and corresponding
frequencies are shown (Fig. 1.5).

Note: + and – signs indicate the motion of the corresponding atom, above and below
the plane of the paper respectively.

Of the four normal modes of vibration of C02, only three are IR active. The
asymmetric stretching and two bending vibrations involve change in dipole moment so they
are IR active. But the symmetric stretching vibration does not involve any change in the
dipole moment (IR inactive).

Thus, though there are three active vibrations, two of them (two bending vibrations)
have the same frequency, so the IR spectrum of CO 2 exhibits only two bands i.e. one at 666
cm-1 for bending vibration and another at 2350 cm–1 for asymmetric stretching.

Applications of IR spectroscopy

1. Identity of the compound can be established

The IR spectrum of the compound is compared with that of known compounds. From
the resemblance of the two spectra, the nature of the compound can be established. This is
because a particular group of atoms gives a characteristic absorption band in the IR spectrum.

Eg: - IR spectra of both benzaldehyde and phenyl methyl ketone

show a sharp absorption peak at 1700 cm-1.This indicates the presence of C

= O group in both the compounds.

2. Detection of functional groups

16
 In a given environment, a certain functional group will absorb IR energy of very
nearly the same wavelength in all molecules.

Eg. (i) Acetone and diethyl ketone give absorption

peak at the' same place.

(ii) But, acetic acid (CH 3COOH) and cyclobutanone give absorption
peak at different places.

3. Testing purity of a sample

Pure sample will give a sharp and well - resolved absorption bands. But impure
sample will give a broad and poorly resolved absorption bands. Thus by comparison with IR
spectra of pure compound, presence of impurity can be detected.

4. Study of progress of a chemical reaction

The progress of a chemical reaction can be easily followed by examining the IR

spectrum of test solution at different time intervals.

5. Determination of shape or symmetry of a molecule

Whether the molecule is linear (or) non-linear (bend-molecule) can be found out by
IR spectra. According to the following calculations,

(i) For non-linear molecule = (3n–6) = 3 peaks.

(ii) For linear molecule = (3n –5) =4 peaks.

Eg. IR spectra of NO2 give three peaks at 750, 1323, and 161.6 cm-1. Since the spectra shows
only 3 peaks, it is confirmed that NO2 molecule is a nonlinear (bend) molecule.

6. Determination of force constant (k)

A simple harmonic oscillator can be considered as a model for vibrating diatomic

molecule. Consider two atoms of masses m1 and m2 connected by means of chemical bond of
force constant k. According to classical mechanics the fundamental frequency of vibration ν 0
is given by

ν0 = 1/ 2π √ k/μ where μ is the reduced mass of the system is given by μ = m1m2 / m1+ m2

k = 4 π2 ν02 μ

In IR spectroscopy ν0 = ν and ν = c ν

17
 k = 4 π2 c2 (ν) 2 μ

Problems

The CO molecule absorbs infrared frequency of 2140cm -1. Calculate the

force constant of the chemical bond, given that atomic masses of C= 12 amu
and O = 16amu.
k = 4 π2 ν02 μ

μ = m1m2 / m1+ m2

= 12x 1.66 x 10-27kg x 16x 1.66x10-27kg / 12x1.66 x 10-27kg x 16x 1.66x10-27 kg

= 1.4 x 10-26kg

Frequency of absorbed IR radiation (ν) is equal to fundamental vibrational frequency of the

molecule (ν0)

k = 4 π 2 ν2 μ

ν=cν

k = 4 π 2 c 2 ν2 μ Given that ν = 2140cm-1

k = 4 x 3.142 x (3x108ms-1)2 x (2140x102 m-1)2 x 1.14x 10-26 kg = 1853Nm-1

1
H - NMR SPECTROSCOPY
Principle

NMR (Nuclear Magnetic Resonance) is a powerful tool 'for investigating nuclear

structure of atoms and molecules. In NMR, radio frequency waves (60- 500 MHz) induce
transitions between magnetic energy levels of nuclei of a molecule. The magnetic energy
levels are created by keeping the nuclei in a magnetic field.

A nucleus with spin ½ will have two possible orientations. In the absence of external
magnetic field, these orientations are of equal energy. If a magnetic field is applied, then the
energy level split.

For instance, the nucleus of hydrogen (proton) spins about its own axis. Due to its
positive charge, the spinning proton generates a magnetic moment and behaves like a tiny bar
magnet. If the proton is placed in a strong magnetic field, the two energy levels become
separate. But, in the absence of external magnetic field the energy levels are equal.

The energies of these two states are represented in the following figure.

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 Two energy levels of the nucleus

A transition from the low energy state E1 to the high energy state E2 can be obtained by
providing an energy equal to the difference in energy between the two states,

If the nucleus lies in the upper energy state, E 2, that will come to lower energy state,
E1 by emitting energy corresponding to (spin –spin relaxation)

The frequency absorbed or emitted by a nucleus in moving from one energy level to
another is directly proportional to the applied magnetic field and gives the NMR spectrum.
Thus, NMR spectrum is plotted between absorption signal at the detector and the strength of
the magnetic field Ho

Resonance

When a nucleus is placed in a system, it absorbs energy and goes to the excited state.
Then it loses energy and returns to unexcited state. Again it absorbs energy and goes to
excited state. Thus, the nucleus which alternately becomes excited and unexcited is said to be
in a state of resonance.

NMR Activity of atoms

Nuclei with spin quantum number I greater than zero shows NMR activity.

NMR deals with nuclei having I= ½. Spin quantum number I related to atomic no. and mass
no. of nucleus. Sub atomic particles (e, p & n) can be imagined as spinning on their axes. In
most of the atoms these spins are paired against each other (C 12), such that the nucleus of the
atom has no overall spin. However, in some atoms ( 1H1, C13 etc.) the nucleus does possess an
overall spin. The rules for determining the net spin of the nucleus are as follows

1. Nuclei with odd atomic number (Z) and odd mass number (A) are active eg; - 1H1,
15 31
7N , 15P etc.

2. Nuclei with odd atomic number (Z) and even mass number (A) are active. Eg; - 1H2,
14 10
7N , 5B etc.

3. Nuclei with even atomic number (Z) and odd mass number (A) are active. Eg; - 6C13
etc.

Nuclei with even atomic number (Z) and even mass number (A)
have no magnetic moment, so NMR inactive. Eg; - 6C12, 2He4, 8O16 etc.

Atomic no. Mass no. Spin eg Activity

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 odd odd 1/2 1H1,7N15, 15P31 active

odd even 1/2 1H2,7N4,5B10 active

even odd 1/2 6C13 active

even even 6C12, 2He4, 8O16 inactive

Chemical shift
In NMR spectroscopy, the chemical shift is the resonant frequency of a nucleus
relative to a standard. The shift in the position of NMR signals (compared with a standard
reference) resulting from the shielding and deshielding by electrons are referred to as
chemical shift.

Chemical shift is the difference between the resonance frequency of the observed
proton and TMS (Tetra methyl silane). TMS is the common reference compound in NMR, its
=0

The position of NMR signal gives an idea about the kinds of proton. (Like aliphatic,
aromatic, primary, secondary). Different kinds of protons in different electronic environments
give different peaks in NMR. This difference is represented by chemical shift . Chemical
shifts have values from 0- 10

Causes of Chemical shift

When a molecule is placed in a magnetic field its electrons are caused to circulate and
thus they produce a secondary magnetic field. This induced magnetic field may oppose or
reinforce the applied field. Thus the two possibilities are

1. Shielding

If the induced magnetic field opposes the applied magnetic field, the net magnetic
field felt by the nucleus, in a molecule, will be less than the applied (external) magnetic field
and the nucleus is said to be shielded. High electron density at around a nucleus shields the
nucleus from the external magnetic field. The more shielded a proton is, the greater must be
the strength of the applied field in order to produce an absorption signal. Thus, the NMR
signals are up field (lower 5 value) in the NMR spectrum.

2. Deshielding

If the induced magnetic field reinforces the applied magnetic field, the net magnetic
field felt by the nucleus in a molecule will be more than the applied magnetic field and the
nucleus is said to be de shielded. Low electron density at around a nucleus deshields the

20
nucleus from the external magnetic field. Thus, the NMR signals are down field (higher 8
value) in the NMR spectrum.

Measurement of chemical shift

Instead of measuring chemical shift in absolute terms, we measure them with respect to
standard Tetra methyl silane (CH3)4Si abbreviated as TMS.

Reasons for taking TMS as standard

1. TMS has 12 equivalent protons and gives an intense sharp single signal which appear
at higher field than most of the organic compounds due to lower electronegativity of
Si than C

2. TMS is chemically inert, highly volatile and has a very low boiling point. So it can be
easy removed by evaporation after the spectrum has been recorded.

3. It is soluble in most of the organic solvents and can be added to the sample solution as
an internal standard.

Methods of expressing chemical shift

The position of signal in NMR spectrum relative to a reference signal is expressed in terms of
chemical shift , which is defined as

In terms of frequency

Ppm

Chemical shift ‘ ’, is dimensionless and is expressed in ppm. Chemical shift have values
from 0-10. 1MHz = 106 Hz

Factors affecting chemical shift

The followings are important factors that influences chemical shift.

1. Electron density

It shields a nucleus from the external field.

2. Electronegativity of neighbouring group

Electronegative groups attached to the -CH group, decrease the electron density
around the protons, and there is deshielding and the chemical shift increases. Thus, the
chemical shift increases with increase in electronegativity of the bonded atoms.

I < Br < CI < F

3. Magnetic anisotropic effect

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 Anisotropy means non-uniform, magnetic anisotropy is the non-uniform magnetic
field. Electrons present in the π- systems (alkenes, alkynes, aromatics, etc.,) interact with the
applied magnetic field causes anisotropy. It causes both shielding and de shielding effects.

4. Hydrogen bonding

Presence of hydrogen bonding changes the chemical shift values. The more hydrogen
bonding, more protons are deshielded and the chemical shift increases.

Proton NMR (1HNMR) spectroscopy

The most common form of NMR is based on hydrogen ( 1H) nucleus or proton. It can give
information about the structure of molecule containing hydrogen atoms

Interpretation of NMR signals

Protons in an organic molecule may give NMR signal at the applied magnetic field.
The NMR signal consists of many- absorption peaks, whose relative positions give
informations about the molecular structure.

1. The number of signals indicates the presence of different kinds of protons in a

molecule.

2. The position of the signals gives the information about the electronic environment of
each kind of proton.

3. The intensities of the signals are measured from the area under each peak, from which
we may know how many protons of each kind are there.

4. Splitting of signals into several peaks in an NMR spectrum tells us about the atoms
present in neighbouring groups.

Example
1
1. H-NMR spectra of benzene

Benzene gives a single peak at 7.26 ppm, which shows that the 6 hydrogen atoms in
benzene ring are equal.

1
2. H-NMR spectra of acetaldehyde

In acetaldehyde there are two types of protons in two different environments.

The three protons in – CH3, have identical chemical environments and so all absorb at
the same energy

22
 But, the proton in –CHO is in different chemical environment and it absorbs at
different energy. The intensity of the –CH3 peak is three times the intensity of the –CHO
peak.
1
3. H -NMR spectra of ethanol

In ethanol, there are three types of protons in three different environments. The three
protons in –CH3, have identical chemical environments and all absorbs at the same energy.
The protons in –CH2 is in different chemical environment and it absorbs at different energy.
But, the protons in - OH, absorbs at different energy. Thus, CH 3CH2OH gives three NMR
signal.

Spin-Spin splitting (spin-spin coupling)

The NMR spectrum of any compound at low resolution gives broad signal. But the
same at high resolution causes further splitting of NMR signal by spin-spin interaction.
Further splitting of the NMR signal due to the interaction between protons on adjacent atoms
is referred to as spin-spin splitting (or) coupling.

Conditions for spin-spin coupling

1. Chemically equivalent protons will not cause spin-spin coupling. Non-equivalent

protons only will couple.

2. Protons present in an adjacent carbon atom will couple.

3. Protons present in the carbon atom, having multiple bonds, will not couple.

4. Protons separated by four or more bond will not couple.

n +1 rule

The multiplicity of a signal can be calculated by using n + 1 rule. If n number of

protons are present in a nearby nucleus, the peak will split into n + 1 lines. When a group of
protons have different chemical environment on either side, (n+ n1) + 1 lines are observed.

23
 If no hydrogen is present in neighbour atom, then n + 1 = 0 + 1 = 1 (gives singlet peak)

If one hydrogen is present in neighbour atom, then n+ l = 1+1=2 (gives doublet peak)

If two hydrogens are present in neighbour atom, then n + 1 = 2+ 1=3 (gives triplet peak)

The relative intensities of different signals can be obtained with the help of Pascal’s
triangles.

No. of signals No.of protons Splitting pattern Name

causing splitting
(relative intensities)

1 0 1 Singlet

2 1 1 1 Doublet

3 2 1 2 1 Triplet

4 3 1 3 3 1 Quartet

5 4 1 4 6 4 1 Quintet

Examples

1. Proton NMR spectra of ethanol (CH3-CH2-O-H)

In ethanol, the peak for - CH 3 is further splits into triplet due to the 2 protons present
in the adjacent carbon atom (n + 1; 2 + 1 = 3 signal). Similarly, the peak for - CH 2 is splits
into quartet, this is due to the 3 protons present in adjacent -CH 3 (n + l; 3 + l =4 signal). But,
there is no spin - spin interaction between the - OH proton and other protons.

2. Proton NMR spectra of ethyl bromide (CH3-CH2-Br)

24
 In ethyl bromide there are two types of protons -CH3 and -CH2. The -CH3 protons
give peak at lower value near the standard TMS. But, the -CH2 protons give peak at higher
value due to the influence of electronegative atom Br.

CH3 protons further split into triplet, this is due to the influence of two protons present
in the adjacent carbon atom (- CH2) (n + 1; 2 + 1 = 3 signal). Similarly, CH 2 protons split into
quartet this is due to the 3 protons present in adjacent –CH3 group (n + 1; 3 + 1 = 4 signal)

Coupling constant

Coupling constant is the distance between the two peaks in a given multiple NMR
signal. It is denoted by the symbol J and expressed in Hz.

Problem1; - Predict the number of signals, peak ratio, their relative positions,
multiplicity and relative intensity ratio of the following compound.

Ethanol- CH3-CH2-OH

No. of peaks = 3 (due to 3 types of protons)

Peak ratio = 3: 2: 1 (no.of protons in each type)

Multiplicity; -

i) –CH3 protons split into triplet in the ratio 1:2:1due to the presence of 2 protons
in nearby atom

ii) –CH2 protons split into quartet in the ratio 1:3:3:1due to the presence of 3
protons in nearby atom

iii) –OH appear as a singlet as there is no spin –spin interaction between OH

proton and other protons.

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Applications of NMR spectroscopy

1. Structural diagnosis by NMR

The structure of an unknown compound from its NMR spectrum can be confirmed.

Examples

(i) The number of main NMR signals should be equal to the number of equivalent
protons in the unknown compound.

(ii) The chemical shifts indicate that what type of hydrogen atoms is present.

(iii) From the area of peaks, the number of hydrogen present in each group can be known.

2. Quantitative analysis

NMR spectroscopy is used to determine the molar ratio of the components in a

mixture.

3. Hydrogen bonding

It is used to study the hydrogen bonding in metal chelates and organic compounds.
■

4. Elemental analysis

It is used for the determination of total concentration of a given kind of magnetic

nucleus in a sample.

5. Study of isotopes other than proton

Several nuclei, in addition to proton, which have magnetic moments, can be studied
by the NMR technique.

6. Keto-enol Tautomerism

It is useful in studying keto-enol tautomerism.

Magnetic Resonance Imaging (MRI)

Principle

The basic principle of MRI and NMR is the same. The machine of MRI makes use of
the fact that the body tissue contains lot of water, the protons (H 1) of which get aligned in a
large magnetic field. When a person is placed inside the powerful magnetic field of the
machine, the protons align -themselves with the direction of the magnetic field. This external
magnetic field, applied on the nuclei, produce energy levels.

Then, a radio frequency waves, called resonance frequency, is applied perpendicular

to the magnetic field, causes transitions between these levels. When such a radiation is
absorbed, the nuclei are converted into an excited state. If the radio frequency (RF) waves are
removed, the nuclei will re-emit the absorbed radiation. This process is known Relaxation.
Thus, the signal produced during relaxation is known as the free-induction decay (FID)

26
response signal. The FID response signal is measured by a conductive field coil placed
around the object being imaged. This measured signal is processed to obtain 3D MR images.

MRI is used to diagnose or monitor the treatment conditions like Tumors of

the chest, liver related diseases, heart problems, inflammatory bowel disease.

University questions Module I- Spectroscopy

Part A - Each question carries 2 marks

1. The absorbance of a 0.01M dye solution in ethanol is 0.62 in a 2cm cell for
light of wavelength 5000A . If the path length of light through the sample is doubled and
0

the concentration is made half, what will be the value of absorbance?

2. Which of the following molecules can give IR absorption? Give reason. a) O 2 b) HCl
c) N2 d) CO2
3. How many modes of vibrations are there in water molecule? State weather all are
IR active?

4. Which of the following molecule can give an IR spectrum? Give reason. (a)H 2 (b)
N2 (c) HCl (d) Cl2

5. Chemical shift value of methyl chloride is lower compared to that of methyl

fluoride. Why?
6. Which of the following nuclei do not show NMR spectrum? Why? 1H, 12C, 19F,16O,14N
7. Calculate the fundamental vibrational frequency HCl molecule, if the value of force
constant of the molecule is 483 Nm-1. The atomic masses are 1H = 1.673 x 10-27 kg
and 35Cl = 58.06 x 10-27 kg.
Part B - Each question carries 3 marks
1. Write three points of comparison between UV and IR spectrum.

2. The fundamental vibrational frequency of CO is 2140cm -1. Calculate force constant of the
bonds if reduced mass of CO is 1.14 x 10-26 Kg.
3. Why is TMS taken as reference to determine chemical shift value in NMR spectroscopy?

5. List all the electronic transitions possible for CH3Cl and HCHO.
6. List the electronic transitions possible when UV light is absorbed by the
following molecules. i) CH4 ii) CH3Cl iii) HCHO
7. State and explain Beer- Lamberts law. Mention any two limitations of the law.

Part C- Each question carries 10 marks

1.(a) Why does a signal for a particular set of protons split into a multiplet? Give number of
signals, peak ratio and multiplicity of different sets of protons in the NMR spectrum of 1-
bromopropane.
(b) Give a neat and labelled sketch of instrumentation of UV-visible spectrometer.

27
(c) Write a note on vibrational modes of carbon dioxide molecule. State which of these
modes are IR active; and give reason for their activity. (4+3+3)
2. (a) What is chemical shift? Write the cause of chemical shift.
(b) CO molecule absorbs at 2140cm-1. Calculate the force constant of the molecule, given
atomic masses of C and O are 12u and 16 u respectively 1u =1.67 x 10-27kg.
(c) What are the various energy transitions possible in a molecule? Why does electronic
spectrum appear broad? (4+3+3)

3. a) Explain Spin-Spin splitting. Write the splitting pattern in the NMR spectrum of CH 2Cl –
CH2 –CH2Cl.

b) Explain the various modes of vibrations possible for H 2O. Which of them are IR active? Give
reasons.

c) A solution shows a transmittance of 20 % when taken in a cell of 2.5cm thickness. Calculate its
concentration if the molar absorption coefficient is 12000 dm2mol-1 (4+3+3)

4. a) What is Chemical Shift? Explain Shielding and Deshielding

b) Give a neat labelled sketch of UV-Visible Spectrometer. (6+4)
5. (a)Write the mathematical representation of the law governing absorption of light by
molecules of a solution. A dye solution of concentration 0.05M shows an absorbance of
0.055 at 540nm while a test solution of the same has an absorbance of 0.025 under same
conditions. Calculate concentration of test solution.
(b) What is meant by the term shielding in NMR spectroscopy? Arrange the CH3F, CH3Cl,
CH3Br and CH3I in the increasing order of shielding effect. Give the reason for your answer.
(c) Give the reason for high δ-value of aromatic protons. (3+3+4)
6. (a) Define IR spectrum. Why HCl is IR active, but hydrogen molecule is not. Write the
reason for the statement.
(b) What is meant by spin-spin coupling in NMR spectroscopy? Predict the different types
of protons, the number of signals and the ratio of area of peaks in the NMR spectrum of
CH3-O-CH2-CH3
(c) What is MRI? How is it useful in the field of medicine? (3+4+3)
7. (a) State the principle of vibrational (IR) spectroscopy. Arrange the following bonds in the
order of increasing stretching frequencies C-C, C=C and CΞC; Write suitable explanation for
your answer. (5)
(b)What is spin-spin splitting? Write the splitting pattern in the NMR spectrum of CH2Cl-
CH2- CH2Cl. (3)
(c)Write two important applications of electronic spectroscopy. (2)
8. (a) Explain the principle of NMR spectroscopy. Which of the following nuclei can have a
presence in NMR spectrum? (i)16O8 (ii) 13C6 (iii) 2H1 . Reason for your answer. (4)
(b) Define chemical shift. Interpret the number of signals, the position of signals and the
intensity of signals in the NMR spectrum of CH3CH2CH2Cl. (4)

28
(c) Most absorption bands in the electronic spectra are very broad. Give reason. (2)
. a) Explain Spin-Spin splitting. Write the splitting pattern in the NMR spectrum of CH 2Cl –
CH2 –CH2Cl.
b) Explain the various modes of vibrations possible for H 2O. Which of them are IR active? Give
reasons.
c) A solution shows a transmittance of 20 % when taken in a cell of 2.5cm thickness. Calculate
its concentration if the molar absorption coefficient is 12000 dm2mol-1 (4+3+3)
10. a) What is Chemical Shift? Explain Shielding and Deshielding
b) Give a neat labelled sketch of UV-Visible Spectrometer. (6+4)
11. (a) Predict the splitting pattern in the nmr spectra of CH3CH2COOCH3and CH3CHCl2.
(b)The fundamental vibrational frequency of carbon monoxide ( 12C16O) is 2140 cm . Without
-1

calculating force constant, find the fundamental frequency of 13C17O in cm . [5+5]

-1

12. (a) Which among the following molecules will give n→π* transition.
C2H6, CH3CHO, C6H5CONH2, C2H5OH, C2H4. Rationalize your answer.

b) Briefly explain chemical shift and factors affecting it. [5+5]

13. a) Draw the structure of the following compounds satisfying the given NMR spectral data: -
i) C3H7Cl – one doublet (6H) and one septet (1H)
ii) C4H10O- one singlet (3H), one doublet (6H) and one septet (1H)
b) Predict the number of signals in the NMR spectrum of the following compounds? i)
Cyclobutane ii) 1,2- Dichloro ethane iii) 2-Chloropropane iv) Vinyl chloride. [6 + 4]

14. a) Write the principle behind IR spectroscopy b) How will you distinguish between
intermolecular and intramolecular hydrogen bonding using IR spectroscopy?

b) What are the different kinds of electronic transitions possible in organic molecules? Give two
applications of UV-Visible spectroscopy. [5+5].
15. a) Outline the principles of IR spectroscopy. [5]
b) How will you distinguish ethanol and dimethyl ether using NMR spectroscopy? [5]
16. a) Define chemical shift in NMR spectroscopy. Also explain the factors influencing
chemical shift. [5]
b) Discuss the possible electronic transitions in acetaldehyde. [5]

29
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