Department of Chemistry

B.Sc. (V Semester): PCM and CBZ (CBCS Scheme)

CHEMICAL SPECTROSCOPY
BY Dr. NN

General Introduction: Electromagnetic radiations

To explain some important phenomena like interference, refraction, diffraction etc.,
most concerns us here and we shall see that the propagation of light by light waves involves
both electric and magnetic forces. This gives rise to their common name electromagnetic
radiation.

Representation of light waves travelling though space:

Wave length (λ): It is the distance between the two adjacent crests or troughs in a particular
wave.
Wave length in meters (m)
10-6 = 1 micro meter (1μm)
10-9 = 1 nano meter (1nm)
Wave number (ν): It is the reciprocal of wavelength or most frequently number waves per
cm.
If the wave length of light radiation is known, the corresponding wave number can be
calculated.
Example: λ=2.5×10-4cm, wave number =1/ λ=1/2.5×10-4=4000cm-1

Summary of spectroscopic techniques in organic chemistry and

information obtainable from each:

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Radiation absorbed Effect on the molecule (and information deduced)

Uv-Visible Changes in electronic energy levels with in the molecule

(Extent of ∏-electron systems, presence of conjugated
λ 190-400nm and 400-800nm unsaturation, and conjugation with non-bonding electrons)

Infrared Changes in the vibrational and rotational movements of the

molecule(detection of functional groups , which have
λ 2.5-25μm specific vibrational frequencies- for example: C=O, NH2,
γ 400-4000m-1 OH etc.,

Microwave Electron spin resonance or electron paramagnetic

resonance: induces changes in the magnetic properties of
γ 9.5×109Hz unpaired electrons (detection of free radicals and the
interaction of the electrons with. For ex. Nearby protons

Radiofrequency Nuclear magnetic resonance induces changes in the

magnetic properties of certain atomic nuclei notably that of
γ 60 – 600 MHz hydrogen and the 13C isotope of C (hydrogen and carbon
atoms in different environments can be detected and
counted etc.,

Electron beam impact Ionization and fragmentation of the molecule into a

spectrum of fragment of ions (determination of molecular
70ev, 6000KJ/mole weight and deduction of molecular structure).

Types of Spectroscopy:
I) Nuclear Magnetic Resonance -- magnetic environment in which nucleus is found

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 – Total structure determination
II) Infrared -- types of bonds found in the molecule
– Functional group determination
III) UV-Vis -- degree of conjugation
– Double bonds
IV) Mass Spectroscopy
– Determination of MW of compound and fragments

Nuclear magnetic resonance spectroscopy (NMR):

NMR spectroscope is discovered by the American physicists, Felix Block (Stanford
University) and Edwerd Purcell (Harward University). They shared the Nobel Prize for their
work in 1952.
NMR is one of the most valuable spectroscopic techniques available to organic
chemists. It is the method of structure determination to which chemists first turn for
information.
NMR does not replace or duplicate either of IR, UV or mass spectroscopic techniques;
rather, it complements them. It provides a map of the carbon-hydrogen frame work of an
organic molecule. Taken together these techniques often allow us to obtain complete
solutions for the structure of even complex unknown.
NMR as is implied in the name, concerned with the magnetic properties of certain
atomic nuclei.
Two types of NMR spectroscopy in common use today are notably hydrogen atom- the
proton and that of the carbon-13, isotope of carbon. By studying a compound by NMR, one
can obtain the following information.
1. The number of signals: This tells us how many different kinds of protons are there
in a molecule.
2. The position of the signals: This tells us something about the electronic
environment of each kind of protons.
3. The intensities of the signals: This tells us how much number of different kinds of
protons is there.
4. Coupling constants: This gives us further information on molecular structure and
stereo chemical features.

Magnetic properties of nuclei:

a) Nuclear magnetic moment:

The nuclear magnetic moment is the magnetic moment of an atomic nucleus and
arises from the spin of the protons and neutrons. It is mainly a magnetic dipole moment; the
quadrupole moment does cause some small shifts in the hyperfine structure as well.
The nuclear magnetic moment varies from isotope to isotope of an element. It can
only be zero if the numbers of protons and of neutrons are both even.
According to the shell model, protons or neutrons tend to form pairs of opposite total
angular momentum. Therefore the magnetic moment of a nucleus with even numbers of both

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protons and neutrons is zero, while that of a nucleus with an odd number of protons and even
number of neutrons (or vice versa) will have to be that of the "last", unpaired proton (or
neutron). For a nucleus with odd numbers of both protons and neutrons, the total magnetic
moment will be some combination of the magnetic moments of both of the "last", unpaired
proton and neutron.

b) Nuclear Spin:
It is the total angular momentum of an atomic nucleus resulting from the coupled spin
and orbital angular momenta of its constituent nuclei. It is also known as nuclear angular
momentum. Symbolized I.

The effect of an external Magnetic field:

Many kinds of nuclei behave as if they were spinning about an axis. Since they are
positively charged, these spinning nuclei act like tiny magnet. The particle generates a
magnetic field and the nucleus of hydrogen is no exception. These spinning nuclei can
interact with an externally applied magnetic field (HO). In the absence of strong external
magnetic fields, the nuclear spins of magnetic nuclei are oriented randomly. When these
nuclei are placed between the poles of a strong magnet, however, they adopt two specific
orientations with respect to an external magnetic field; either aligned with the field (the lower
energy state) or opposed to the field (the higher energy state). We can also describe these
orientations as parallel with or anti-parallel with the applied field.

Nuclear Spins in Zero Field: Within a collection of1H or 13C atoms, nuclear spins are
completely random in orientation.

The number of allowed nuclear spin states does not change.

Nuclear Spins in B0 : When placed in an external magnetic field of strength B0, only certain
orientations of nuclear magnetic moments are allowed.

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 B0

Nuclear Magnetic Resonance

When nuclei with a spin quantum number of 1/2 are placed in an applied field, a small
majority of nuclear spins are aligned with the applied field in the lower energy state.
If a nucleus is irradiated with electromagnetic radiation of the appropriate energy, the
energy is absorbed, and the nuclear spin is flipped from spin state +1/2 (with the applied
field) to -1/2 (against the applied field).

Resonance:
It is the absorption of electromagnetic radiation by a nucleus and flip of its nuclear
spin from a lower energy state to a higher energy state. The instrument detects this and
records it as a signal.

Theory of NMR:
The nuclei which has the spin quantum number I>0 only exhibit NMR phenomenon.
The spin quantum number I associated with the mass number and the atomic number is as
follows.

Mass number Atomic number Spin quantum number

Odd Odd or Even 1/2, 3/2, 5/2

Even Even 0

Even Odd 1, 2, 3, …..

Common Magnetic nuclei Common non-magnetic nuclei

1
H, 13C (most important) 12
C, 16O, 32S
2H, 11B, 14N, 19F, 31P

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Under the influence of an external magnetic field, a nucleus can take up different orientations
with respect to that field. The number of possible orientations is given by (2I+1).

Spin quantum number No. of Orientations Examples

1
½ 2 H, 13C, 19F, 31P
2
1 3 H, 14N
11
3/2 4 B, 35Cl

In an applied magnetic field, the magnetic nuclei like the proton precess at a
frequency γ, which is proportional to the strength of the applied field. The exact frequency is
given by
√𝐇𝟎
γ=
𝟐∏
Where, H0 = the strength of external magnetic field, and √ = the Gyromagnetic ratio.

Saturation and Relaxation process:

Nuclei in the lower energy undergo transitions to the higher energy state, the population
of the two states may approach equality and no more energy could be absorbed. The intensity
of the absorption signals may diminish and may under certain circumstances vanish entirely.
This is known as Saturation. Fortunately, there exists a mechanism whereby the nucleus in
the higher energy state can lose energy to its environment and thus return to its lower energy
state. This is called Relaxation process. There are two types of relaxation process.

CHEMICAL SHIFT:

The difference in the absorption position of a particular proton from the absorption
position of a reference proton is called the chemical shift of the particular proton.

We now have the concept that proton in different chemical environment have different
chemical shifts. Conversely, protons in the same chemical environment have the same
chemical shift.
Low field high field
Down field up field
Deshielded Shielded

TMS

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 O
High frequency side applied field low frequency side

NMR scale:
(Delta) or (Tau) scales are used to measure chemical shift. In majority of organic
compounds, protons resonate at a lower field than the protons of tetramethyl silane (TMS).
Thus assigning delta() value for TMS equal to zero, a scale can be defined in which most
proton resonances are of the same sign. Any proton or set of protons which absorb at a field
lower than TMS is given a positive value for , Tetramethyl silane is the most convenient
reference.
𝛄𝐬𝐚𝐦𝐩𝐥𝐞 − 𝛄𝐫𝐞𝐟𝐞𝐫𝐞𝐧𝐜𝐞
=
𝐨𝐩𝐞𝐫𝐚𝐭𝐢𝐧𝐠 𝐟𝐫𝐞𝐪𝐮𝐞𝐧𝐜𝐲 𝐢𝐧 𝐦𝐞𝐠𝐚𝐜𝐲𝐥𝐞𝐬(𝐩𝐞𝐫 𝐬𝐞𝐜. )

∆𝛄
=
𝐨𝐩𝐞𝐫𝐚𝐭𝐢𝐧𝐠 𝐟𝐫𝐞𝐪𝐮𝐞𝐧𝐜𝐲 𝐢𝐧 𝐦𝐞𝐠𝐚𝐜𝐲𝐥𝐞𝐬(𝐩𝐞𝐫 𝐬𝐞𝐜. )

Where, ∆γ is the frequency shift. The value of  is expressed in parts per million (ppm). Most
chemical shifts have  values between 0 and 10. In the scale, signal for the standard
reference, TMS is taken as 10ppm. The two scales are related by the expression
 = 10 - 
NMR signal is usually plotted with magnetic field strength increasing to the right. Thus,
the signal for TMS (highly shielded) appears at the extreme right of spectrum with  = 0 ppm.
Greater the deshielding of protons, larger will be the value of . For most of the organic
compounds, signals appear downfield to the left of TMS signal. The value of chemical shifts
for protons in different environments are:

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 TMS
Highly shielded signals Upfield

Deshielded signals Downfield

10 9 8 7 6 5 4 3 2 1 0

Chemical shift

 - Scale

0 1 2 3 4 5 6 7 8 9 10

Chemical shift
γ - Scale

Use of TMS as solvent/Internal standards: The most generally useful

reference compound as internal standards is Tetra Methyl Silane (TMS). It has several
advantages.
1. It is chemically inert.
2. It is magnetically isotopic.
3. It absorbs at higher field than almost all organic protons.
4. It gives a single sharp peak.
5. It is volatile (bp 27˚C) so that it can be easily removed from a sample of valuable
organic compound.
6. It is soluble in most of the sample solution (0.01 to 1.0%) as an internal standard.
When H2O or D2O is the solvent, TMS can be used as an external reference. i.e., it can
be used in a sealed capillary immersed in the solution.

Factors influencing chemical shift:

Shielding and Deshielding: Circulation of electrons about the proton itself generates a field.
If it opposes the applied field, then the field felt by the proton diminished and the position is
said to be shielded. If the field reinforces the applied field, then the field felt by the proton is
augmented and the proton is said to be deshielded.
The following are the factors which influences the chemical shift.
(a) Inductive effect
(b) Vander Waal’s deshielding
(c) Anisotropic effect
(d) Hydrogen bonding
(a) Inductive effect:
A proton is said to be deshielded if it is attached to an electromagnetic atom or group.
Grater the electronegativity of the atom, grater is the deshielding caused to the proton. If the
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deshielding is more for a proton, then its  value will be more. Consider the following
compounds:
(i) CH3-CH2-F (ii) CH3-CH2-Cl
b a b a
Two signals are expected for each of the two compounds. Deshielding for protons ‘a’ in
compound (i) is more than that for similar protons in compound (ii).
As the distance from the electronegative atom increases, the deshielding effect due to it
diminishes. Protons ‘b’ are comparatively less deshielded and hence will resonate at
comparatively lower value of .
CH3-F CH3-Cl CH3-Br CH3-I
4.26 3.0 2.82 2.16
Similarly,
CH3-O- CH3-N- CH3-C
3.3 2.2 0.9
Grater the distance of the electronegative atom or group from a particular proton, smaller is
the deshielding effect on it. For example,
R-CH3 0.9 CH3-Cl 3.0 CH3-C-Cl 1.5
R2-CH2 1.3 R-CH2-Cl 3.4 R-CH2-C-Cl 1.6
R3-CH 1.5 R2-CH-Cl 4.0 R2-CH-C-Cl 1.7
Increasing in number of electronegative atoms or groups to the same carbon atom also leads
to an increase in the deshielding effect.
CH4 CH3-Cl CH2-Cl CH-Cl3
0.9 3.0 5.28 7.24
Unsaturation has a deshielding effect. For example,

H
H C=C H C-C

Protons adjacent to N are very strongly deshielded while those near C are power
fully shielded.
The electron density in the vicinity of alkenic protons is influenced by the electron
withdrawing power of the carbonyl group in α,β - unsaturated carbonyl compounds. This
effect in more prominent at the β-carbon atom of the α,β - unsaturated carbonyl system. As a
result the proton Hb, attached to the β- carbon is deshielded more campared to Ha.

Ha Ha (6.0)
Hb Hb (6.5)

C C C O C C C O

(b) Vander Waal’s deshielding: In a rigid (over crowded) molecule it is possible that
some proton may be occupying sterically hindered position. Clearly, electron cloud of a
bulky group (hindering group) will tend to repel (by electrostatic repulsion) the electron

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cloud surrounding the proton. Thus, such a proton will be deshielded and will resonate at
slightly higher values of  than expected in the absence of this effect. Although this influence
is very small (usually less than 1ppm), it must be borne in mind when predicting the
overcrowded molecules such as highly substituted steroids of alkaloids.
Calculations reveals that the associated shielding contributions for two isolated protons
is negligible if the atoms are separated by more than the sum of their Vander waals radii but
is significant for shorter distances.

Sum of Vander waal radii (A˚) Shielding contribution (ppm)

2.4 0.01

2.0 0.2

1.7 0.5

Spin-Spin splitting in 1H NMR spectra:

From the spectrum of acidified ethanol, it is seen that the methyl absorption is split into
a triplet (relative areas 1:2:1) and the methylene absorption is split into a quartet (1:3:3:1).
The distance between individual peaks in the multiplets is called the coupling constant. And
is denoted by J. Coupling constants are measured in hertz and fall in the range 0-18 Hz. The
exact value of the coupling constant between two groups of proton depends on several
factors.
The spacing of the three components of the methyl group triplet is found to be equal to
the spacing of the four components of the methylene group quartet. The spin-spin splitting
pattern explained by assuming that the magnetic field experienced by the protons of one
group is influenced by the spin arrangements of the protons in the adjacent group. In ethanol,
-OHCH2 proton spins coupled with the CH3 proton spins and appear as a quartet with J=7 Hz.
The CH3 protons appears as a triplet and must have the coupling constant J=7 Hz.

OH-CH2- CH3
H-applied H-applied

The ethanol spectrum illustrates three important rules about spin-spin splitting in 1HNMR.

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1. Chemically equivalent protons do not exhibit spin-spin splitting. The equivalent
protons may be on the same carbon or on different carbons, but their spins still do not
couple; instead, the signal appears as a singlet.
H
H H
Cl C H Cl C C Cl
H
H H

No coupling No coupling

2. A proton that has ‘n’ equivalent neighboring protons gives a signal that is split into a
multiplet of n+1 peaks with coupling constant J.
Protons that are farther than two carbon atoms apart do not usually couple (4bonds).
They show small coupling, when they are separated by ¶ bonds.
H H H H
C C C C C

Coupling observed Coupling not observed

No. of equivalent Type of Ratio of intensities

adjacent protons multiplet
observed
0 Singlet 1

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 1 Doublet 1:1

2 Triplet 1:2:1

3 Quartet 1:3:3:1

4 Quintet 1:4:6:4:1

5 Sextet 1:5:10:10:5:1

6 Septet 1:6:15:20:15:6:1

What is Nuclear Magnetic Resonance (NMR) spectroscopy?

Nuclear Magnetic Resonance (NMR) spectroscopy is (arguably) the most powerful tool
available for determining the structure of organic compounds. This technique relies on the
ability of atomic nuclei to behave like a small magnet and align themselves with an external
magnetic field. When irradiated with a radio frequency signal the nuclei in a molecule can
change from being aligned with the magnetic field to being opposed to it. Therefore, it is
called “nuclear” for the instrument works on stimulating the “nuclei” of the atoms to absorb
radio waves. The energy frequency at which this occurs can be measured and is displayed as
an NMR spectrum. The most common nuclei observed using this technique are 1H and 13C,
but also 31P, 19F, 29Si and 77Se NMR are available.

What is it used for?

To identify and/ or To elucidate detailed structural information about chemical compounds.
For example:
• Determining the purity of medicines before they leave the factory
• Identifying contaminants in food, cosmetics, or medications
• Helping research chemists discover whether a chemical reaction has occurred at the correct
site on a molecule
• Identifying drugs seized by police and customs agents
• Checking the structure of plastics, to ensure they will have the desired properties

How does it work?

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 To get the nuclei in a molecule to all align in the same direction, a very strong
magnetic field is generated using a superconducting electromagnet, which requires very low
temperatures to function. The coils of the magnet are surrounded by liquid helium (4K, or -
269°C), which is prevented from boiling off too quickly by a surrounding layer of liquid
nitrogen (-77°C). These coolants are all contained in double-layer steel with a vacuum
between the layers, to provide insulation just like a thermos. There is a narrow hole through
the middle of the magnet, and the sample tube and radio frequency coils ("probe”) are located
there.

**********

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