Module I

Spectroscopy

Syllabus
Part I-Spectroscopy-Introduction, Beer-Lamberts Law (no derivations) (Numericals).(hours-1)
Part II-UV-Visible spectroscopy- Principle, Instrumentation and applications. (hours-2)
Part III- IR spectroscopy- Principle and applications, Numericals.(hours-2)
Part IV-1 H NMR spectroscopy- Principle, chemical shift- spin spin splitting and applications,
MRI, Spectral problems. (hours-4)

Part I
1. What is spectroscopy?

ˆ Spectroscopy is the analysis of the electromagnetic radiation absorbed, emitted or scat-

tered by molecules.
ˆ Spectral measurement devices are referred to as spectrometers.

2. Differentiate between absorption spectra and emission spectra

Consider two energy levels of an atom or a molecule. The one with lower energy is called
ground state energy level (Eg ) and the one with higher energy is called excited energy level
(Ee ).
ˆ If a photon of frequency hν falls on a
molecule in the ground state and its en-
Ee Ee ergy hν is exactly equal to the energy dif-
ference (∆E=Ee −Eg ) between the two en-
ergy levels, then the molecule undergoes a
hν hν transition from its lower energy level to the
higher energy level with the absorption of
a photon of energy hν. The spectrum thus
obtained is called absorption spectrum.
Eg Eg
Origin of Origin of ˆ If the molecule falls from the excited state
absorption spectrum emission spectrum to the ground state with the emission of
photon of energy hν, the spectrum thus ob-
tained is called emission spectrum.
3. What are the differences between atomic spectra and molecular spectra?

ˆ Atomic spectra arise from the transitions of an electron between the atomic energy levels
ˆ Molecular spectra arise from transitions between rotational and vibrational energy levels
ˆ Atomic spectra can be used to obtain detailed information about the electronic structure
of atoms

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ˆ Molecular spectra give information about the molecular structure, geometry etc.
ˆ Atomic spectra are broader compared to molecular spectra.

4. Why atomic spectra are broader compared to molecular spectra?

ˆ According to Born-Oppenheimer approximation, total energy of a molecule (E) is given

by

E = Etranslational + Erotational + Evibrational + Eelectronic

Furthermore, Etranslational << Erotational << Evibrational <<Eelectronic
Since Etranslational is not quantized and negligibly small,

E ≈ Erotational + Evibrational + Eelectronic

ˆ The electronic transitions in a molecule are invariably accompanied by vibrational and

rotational transitions, the electronic spectra of molecules appear broad.

5. What is Beer Lambet law?

ˆ Beer-Lambert law governs the absorption of radiation by a solution when a monochro-

matic radiation is passed through it.
ˆ It says that the absorbance of light is directly proportional to the path length (l) through
which the light is being transmitted and the concentration of the solution (c).

I0
A = log =cl
It

I
A=Absorbance, T =Transmittance (T= I t ), I 0 = inten-
0
sity of incident radiation. I t = intensity of transmitted
radiation. l= path length, c= concentration of sam-
ple, = molar extinction coefficient or molar absorp-
tivity.  is a constant for a particular solution and
I0 It wavelength. Its unit is M −1 cm−1 or L mol−1 cm−1
c or dm3 mol−1 cm−1 .
By measuring absorbance of sample we can determine
the concentration (c) of species of known molar ab-
l sorptivity () using Beer-Lambert law

6. What are the limitations of Beer Lambert law?

The Beer Lambert law is the linear relationship between absorbance and concentration of
an absorbing species. The linearity of the Beer Lambert law is limited by chemical and
instrumental factors. Causes of nonlinearity include:

ˆ High concentration (>0.01M)

– Deviations in absorptivity coefficients () at high concentration due to electrostatic
interactions between molecules in close proximity
– Changes in refractive index at high concentration
ˆ Scattering of light due to particulates in the sample
ˆ Fluorescence or phosphorescence of the sample
ˆ Non-monochromatic radiation, stray light etc.

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Solved Numerical Problems

S1. The percentage of transmittance of an aqueous solution is 20.5%. The solution has a
molarity 0.001 M. The light passes through the solution present in a 2 cm long cell.
Find the absorbance and molar absorption coefficient of the solution
(Answer: 344.12 M−1 cm−1 )
S2. A solution of thickness 3 cm transmits 20% of the incident light. Calculate the con-
centration of the substance in the solution if the molar absorptivity of the solution is
2000dm3 mol−1 cm−1
(Answer: 1.1649 ×10−4 M)

KTU Examination Questions

K1.1. The absorbance of a 0.01 M dye solution in ethanol is 0.62 in 2 cm cell for light of
wavelength 5000 Å. If the path length of light through the sample is doubled and the
concentration is made half, what will be the value of absorbance?(Jan 2016, 2 Marks)
K1.2. What are various energy transitions possible in a molecule? Why does electronic spec-
trum appear broad?(Jan 2016, 3 Marks)
K1.3. What is a spectrometer? Write the principal components of UV-visible spectrometer
(May/June 2016, 4 Marks)
K1.4. ////////
Derive////////
Beer-/////////////
Lambert’s////////////////////////////////
law(July 2016, 3 Marks)
K1.5. Most absorption bands in the electronic spectra are very broad. Give reason (July 2016,
2 Marks)
K1.6. Write the mathematical representation of the law governing absorption of light by
molecules of a solution. A dye solution of concentration 0.05 M shows an absorbance
of 0.055 at 540 nm while a test solution of the same has an absorbance of 0.025 under
same conditions. Calculate concentration of test solution.(Aug 2016, 3 Marks)
K1.7. A solution shows a transmittance of 20% when taken in a cell of 2.5 cm thickness. Cal-
culate its concentration if the molar absorption coefficient is 12000 dm3 mol−1 cm−1 (Jan
2017, 3 Marks)
K1.8. State and explain Beer-Lamberts law. Mention any two limitations of the law. (Dec
2017, 3 Marks)
K1.9. Calculate the molar absorptivity of 0.5 ×10−5 M dye solution in ethanol which shows
an absorbance of 0.17 when 1.3 cm cuvette is used. (Apr 2018, 3 Marks)

Part II

7. What is UV-Visble spectroscopy?

ˆ It involves the transition of electrons within a molecule or ion from a lower to a higher
electronic energy level or vice versa by the absorption or emission of radiations falling
in the UV-visible range of electromagnetic spectrum (150-400 nm and 400-800 nm).
ˆ As the electronic energy levels are quantized a discrete line should appear in spectra
for every transition. But a discrete line is not obtained since electronic transitions are
accompanied by vibrational and rotational transitions. This leads to the appearance of
bands in the electronic spectra.

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ˆ These broad features are of limited use for sample identification but are very useful
for quantitative measurements. The concentration of an analyte in solution can be
determined by measuring the absorbance at some wavelength and applying the Beer-
Lambert law.

8. Explain the types of electronic transitions possible in a molecule?

According to molecular orbital theory, when a molecule is irradiated with UV or visible
light of appropriate energy, its electrons are promoted from σ and π bonding molecular
orbitals and nonbonding molecular orbitals to antibonding molecular orbitals (σ * and π * ).
σ*
σ → σ* n → σ*
6 6 6

π*
6 6
The possible electronic transitions are
Energy

π → π* n → π*
n σ → σ * , π → π * , n → σ * and n → π *

The order of energy of excitation is

σ → σ*> π → π* > n → σ* > n → π*

π

σ
Possible electronic transitions in a molecule
(a) σ → σ * transitions:-
The σ bonding electrons absorb energy from the electromagnetic radiation and undergo
transition to antibonding σ * orbitals. The transition requires very high energy. There-
fore the absorption occurs in vacuum UV region and do not appear in UV-Vis spectrum.
e.g: alkanes absorb at < 150 nm
(b) π → π * transitions:- This transition occurs in molecules having π electrons.
e.g. alkenes absorb 160-190 nm. Conjugated alkenes absorb at longer wavelength (∼220
nm)
(c) n → σ * transitions:-
Compounds containing nonbonding electrons on O, N, S or halogens show absorption
due to n → σ * transitions.
e.g. methanol absorbs at 183 nm
(d) n → π * transitions:-
Carbonyl compounds (aldehydes, ketones, esters etc.) show absorption due to n → π *
transitions.
e.g. aldehydes and ketones absorb in the range 270-300 nm
9. What are chromophores and auxochromes?

ˆ Chromophores are colour giving groups. They are defined as an isolated covalently
bonded group that shows a characteristic absorption in the UV or visible region e.g.
nitro ( – NO2 ), azo ( – N – N – ), nitroso ( – N – O), nitrile ( – C –– N) etc.
ˆ Auxochromes are colour enhancing groups. They have the capability to extend the con-
jugation of chromophores by sharing nonbonding electrons and thus shift the absorption
band towards the longer wavelength. This shift is called red shift or bathochromic shift.
Auxochromes by themselves do not act as chromophores. e.g: – OH, – OR, – NH2 , – SH
etc.

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10. Explain the instrumentation and working of UV-Vis spectrometer?

Instrumentation

Sample
It Recorder

Monochromator

Detector
Source

Reference
I0

Components

(a) Source:-
Electronic spectra of molecules are obtained by the absorption of molecules from UV
or visible region. Therefore the source which will give electromagnetic radiation in the
above range is selected. A hydrogen discharge lamp produces electromagnetic radiation
in the range of 150-400 nm (UV) and a tungsten filament that gives electromagnetic
radiation in the range 400-800 nm (visible light) are commonly used.
(b) Monochromator:-
Monochromators are used to disperse the radiation according to the wavelength. The
essential elements of a monchromator are an entrance slit, a dispersing element(prism or
grating) and an exit slit. The dispersing element disperses the heterochromatic radiation
into its component wavelengths, whereas the exit slit allows the nominal wavelength to
pass through.
(c) Sample and reference cells:-
The cells (cuvettes) used in UV-visible spectroscopy are made of good quality glass or
quartz and rectangular in shape.
(d) Detector:-
Commonly the detector is either a photographic plate or photomultiplier tube.
(e) Recorder:-
It records the signal received from the detector using a recorder pen.

Working of UV-Vis spectrometer

ˆ The beam from the source is divided into two parallel beams of equal intensity and are
made to pass through the sample cell contains the substance under study dissolved in a
solvent. The reference cell contains the pure solvent.
ˆ The beams from the sample and reference fall on the detector. The detector combined
with an amplifier and a computer can compare the intensities of two beams at each
wavelength in the region.
ˆ The intensity of light coming through the sample is It and that coming from the reference
I
is I0 . The ratio I t is called transmittance (T) and it is commonly expressed in percentage
0
of transmittance.
ˆ The recorder produces a curve where the absorbance or transmittance is recorded as a
function of wavelength, which is called an absorption spectrum.

11. Explain important applications of UV-Visible spectroscopy

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(a) It is used for identifying aromatic compounds and conjugated alkenes:-

This can be used for detection of

impurities. e.g. benzene in cyclo-
hexane
benzene λmax =255 nm naphthalene λmax =280 nm

CH2 CH2 CH2 CH CH CH2

ethylene λmax =165 nm 1,3-butadiene λmax =217 nm As conjugation increases
λmax shifts to longer wave-
CH2 CH CH CH CH CH2 length region.
1,3,5-pentatriene λmax =258 nm
(b) Electronic spectra can be used to identify geometrical isomers:-

H H H Reason is that the extent of con-

C C C C jugation is more in trans isomer
H since the conjugation is hindered by
steric strain in cis isomer e.g. cis-
Stilbene and trans-Stilbene
cis-Stilbene λmax =274 trans-Stilbene λmax =294
(c) To differentiate conjugated and non-conjugated dienes:-
Reason is that conjugation leads to absorption at longer wavelengths
CH2 CH CH CH2 CH2 CH CH2 CH CH2
1,3-butadiene λmax =217 nm 1,4-pentadiene λmax =178 nm
(d) Determination of unknown concentration:-
Absorption spectra in combination with Beer-Lambert law can be used to find out
unknown concentration of substances in solution
(e) Study of kinetics of chemical reaction:-
This is done by measuring concentration of reactant or product with time

KTU Examination Questions

K2.1. Write three points of comparison between UV and IR spectrum(Jan 2016, 3 Marks)
K2.2. Give a neat and labelled sketch of instrumentation of UV-Vis spectrometer(Jan 2016,
3 Marks)
K2.3. What are various energy transitions possible in a molecule? Why does electronic spec-
trum appear broad?(Jan 2016, 3 Marks)
K2.4. Which of the following molecules show UV-Visible absorption? Give reason
i) ethane ii) butadiene iii) benzene iv) phenol (May/June 2016, 3 Marks)
K2.5. What is a spectrometer? Write the principal components of UV-visible spectrome-
ter(May/June 2016, 4 Marks)
K2.6. Write two important applications of electronic spectroscopy(July 2016, 2 Marks)
K2.7. Give a neat labelled sketch of UV-Visible spectrometer(Jan 2017, 4 Marks)
K2.8. List all the electronic transitions possible for CH3 Cl and HCHO(May 2017, 3 Marks)
K2.9. Which among the following molecules will give n → π * transition. C2 H6 , CH3 CHO,
C6 H5 CONH2 , C2 H5 OH, C2 H4 . Rationalise your answer(May 2017, 5 Marks)

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K2.10. Discuss the possible electronic transitions in acetaldehyde. (Dec 2017, 5 Marks)
K2.11. What are the various energy transitions possible for a molecule? (Apr 2018, 4 Marks)
K2.12. Discuss the instrumentation of UV spectroscopy with labelled sketch (Apr 2018, 6
Marks)

Part III
12. What is infrared spectroscopy?

ˆ IR spectroscopy involves transitions between the vibrational energy levels of a molecule

on the absorption of radiations falling in the spectral range of 500 cm−1 − 4000 cm−1 .
ˆ A single vibrational energy change is accompanied by a large number of rotational
energy changes. Therefore IR spectroscopy is also called vibrational spectroscopy or
vibrational-rotational spectroscopy.

13. What is the essential requirement for a molecule to show IR spectrum?

ˆ The essential requirement for a molecule to show IR spectrum is that the dipole moment
must change during vibration.
ˆ Therefore molecules with permanent dipole moment (e.g. NH3 , H2 O, CO, HCl etc.) will
give IR spectra.
ˆ Molecules like CO2 have no permanent dipole moment but dipole moment can be induced
by vibrations also give IR spectra.
ˆ But molecules like O2 , H2 , N2 etc. cannot give IR spectra since they do not have a
permanent dipole moment and a dipole moment cannot be induced by vibration.
ˆ Molecules which give IR spectra are called IR active molecules and the molecules which
do not show IR absorption are called IR inactive molecules.

14. How many modes of vibration are possible for a molecule?

ˆ Molecules which are IR active have different modes of vibration depending upon the
geometry of the molecule and number of atoms in that molecule

ˆ A linear molecule having N atoms will have 3N−5 modes of vibrations. Therefore a
linear diatomic molecule has 3×2−5=1 mode of vibration.

H Cl
stretching
IR active
ˆ A linear triatomic molecule will have 3×3−5=4 modes of vibration. e.g. CO2

O C O O C O
symmetric stretching asymmetric stretching
IR inactive IR active

O C O O C O

bending(in plane) bending(out of plane)

IR active IR active

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ˆ A nonlinear molecule having N number of atoms will have 3N−6 modes of vibra-
tions. Therefore a nonlinear triatomic molecule has 3×3−6=3 modes of vibrations.
e.g.H2 O, H2 S etc.

O O

H H H H H H

O
symmetric stretching asymmetric stretching symmetric bending
IR active IR active IR active
15. Explain the theory of IR spectroscopy

ˆ A simple harmonic oscillator (SHO) can be considered as a model for vibrating diatomic
molecule. The vibrational energy (Evib ) is given by
1
E vib = V + hν0
2
Where V is the vibrational quantum number and has the values 0, 1, 2, 3 etc. ν 0 is the
fundamental vibrational frequency. In the ground state (V=0) above equation becomes
1 1
E vib = 0 + hν0 = hν0
2 2
This energy at the ground state is called zero point energy. Thus even at absolute zero
(0 K) the molecule possesses zero point energy, as the vibration still persists.
ˆ The fundamental vibrational frequency of SHO is given by
s
1 k
ν0 =
2π µ

where k is the force constant and µ is the reduced mass of diatomic molecule which is
given by
m1 m2
µ=
m1 + m2
ˆ To convert this frequency to wave number ν 0 is divided by the velocity of light c in cm
s−1 . s
1 k
ν̄ = cm−1
2πc µ

ˆ From the above equation, it is clear that ν̄ depends upon the bond strength and reduced
mass.
ˆ For example, due to higher bond strength (value of k) of double bond compared to single
bond, C – C stretching is expected to absorb at higher wave number (∼1600 cm−1 ) than
C – C stretching (∼1200 cm−1 ).
ˆ Another example is O – H stretching absorbs at higher wave number (∼3600 cm−1 )
compared to C – C stretching(∼1200 cm−1 ). This is due to smaller value of reduced
mass for O – H compared to C – C

16. What are the important applications of IR spectroscopy?

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(a) Determination of molecular structure:-

The most important application of IR spectroscopy is the identification of structure of
molecules. The region in IR spectra around 500-1500 cm−1 is known as the fingerprint
region since the compounds give unique set of absorption peaks in this region. The
region 1500-4000 cm−1 is known as the functional group region that contains peaks
arising from vibrations of common functional groups in organic molecules.
(b) Determination of force constant:-
The force constant (k) which is a measure of bond strength can be calculated knowing
the absorption wave number (ν̄ )
s
1 k
ν̄ = cm−1
2πc µ

1 k
(ν̄)2 = 2 2
4π c µ
k = 4π 2 c2 (ν̄)2 µ

(c) Determination of purity:-

When a compound is having an impurity it causes the appearance of extra peaks, reduces
the sharpness of individual peaks and a general blurring of the spectrum. For example
small quantities of ketone in hydrocarbons is detected by the appearance of peak near
1720 cm−1 which is the characteristic absorption peak of carbonyl (C – O) group.
(d) To distinguish between intra and inter molecular hydrogen bond:-
This is done by taking a series of IR spectra of the compound at different concentrations.
If the intensity of absorption of O – H stretching for hydrogen bond (3200-3500 cm−1 )
decreases with decrease of concentration, the hydrogen bond is intermolecular. If the
intensity of absorption remains the same with decrease of concentration, the hydrogen
bond is intramolecular.

Solved Numerical Problems

S3. The fundamental vibration frequency of CO is 2140 cm−1 . Calculate the force constant
of the molecule. Given the atomic masses 126C=19.9×10−27 Kg and 168O=26.6×10−27
Kg.
Answer: 1853 Nm−1
S4. Calculate and compare force constants of HCl and HF. Given that observed vibrational
frequency of HCl= 2886 cm−1 and HF=3958 cm−1 . Masses of H, Cl, and F are 1 amu,
35 amu, and 19 amu respectively. 1 amu=1.66×10−27 Kg.
Answer: kHCl =477.59 Nm−1 , kHF =877.78 Nm−1 , kHCl < kHF

KTU Examination Questions

K3.1. Write three points of comparison between UV and IR spectrum (Jan 2016, 3 Marks)
K3.2. Write a note on vibrational modes of carbon dioxide molecule. State which of these
modes are IR active; and give reason for their activity. (Jan 2016, 3 Marks)
K3.3. CO molecule absorbs at 2140 cm−1 . Calculate the force constant of the molecule, given
atomic masses of C and O are 12u and 16u respectively. 1u= 1.67×10−27 Kg. (Jan
2016, 3 Marks)

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K3.4. The vibrational frequency of HCl molecule is 2886 cm−1 . Calculate the force constant
of the molecule. Reduced mass of HCl is 1.63×10−27 Kg. (May/June 2016, 3 Marks)
K3.5. Write the theory of vibrational spectroscopy (May/June 2016, 2 Marks)
K3.6. Sketch the various modes of vibrations possible for CO2 . Which are IR active? Write
reason for your answer(May/June 2016, 5 Marks)
K3.7. Which of the following molecule can give an IR spectrum? Give reason a) H2 b) N2
c) HCl d) Cl2 (July 2016, 2 Marks)
K3.8. State the principle of vibrational (IR) spectroscopy. Arrange the following bonds in
the order of increasing stretching frequencies C – C, C – C and C –– C. Write suitable
explanation for your answer.(July 2016, 5 Marks)
K3.9. How many modes of vibrations are there in water molecule? State weather all are IR
active? (Aug 2016, 2 Marks)
K3.10. Define IR spectrum. Why HCl is IR active, but hydrogen molecule is not. Write the
reason for the statement. (Aug 2016, 3 Marks)
K3.11. Which of the following molecules can give IR absorption? give reason a) O2 b) HCl
c) N2 d) CO2 (Jan 2017, 2 Marks)
K3.12. The fundamental vibrational frequency of CO is 2140 cm−1 . Calculate force constant
of the bond if reduced mass of CO is 1.14 ×10−26 Kg. (Jan 2017, 3 Marks)
K3.13. Explain the various modes of vibrations possible for H2 O. Which of them are IR active?
Give reasons (Jan 2017, 3 Marks)
K3.14. The fundamental vibrational frequency of carbon monoxide ( 12C 16O) is 2140 cm−1 .
Without calculating force constant, find the fundamental frequency of 13C 17O in cm−1 .
(May 2017, 5 Marks)
K3.15. Write the principle behind IR spectroscopy. How will you distinguish between inter-
molecular and intramolecular hydrogen bonding using IR spectroscopy? (July 2017, 5
Marks)
K3.16. Calculate the fundamental vibrational frequency of HCl molecule, if the value of force
constant of the molecule is 483 Nm−1 . The atomic masses are 1H=1.673×10−27 Kg and
35
Cl=58.06×10−27 Kg (Dec 2017, 3 Marks)
K3.17. Outline the principles of IR spectroscopy. (Dec 2017, 5 Marks)
K3.18. Sketch the modes of vibrations possible for CO2 , which are IR active? Give reason.
(Apr 2018, 4 Marks)

Part IV

17. What is nuclear magnetic resonance spectroscopy (NMR Spectroscopy)?

It is a branch of spectroscopy in which radio frequency waves induce transitions between
magnetic energy levels of nuclei of a molecule which are created by keeping the nuclei in a
magnetic field.

18. What are the essential requirement for a nucleus to exhibit NMR phenomenon?

ˆ The nuclei with spin quantum number (I) greater than zero can exhibit NMR phe-
nomenon.

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ˆ In fact any atomic nucleus that possesses odd mass number, odd atomic number or both
has a quantized spin angular momentum and magnetic moment. Common examples are
1 2 13 14 17 19 31
1H, 1H, 6C, 7N, 8O, 9F, 15P etc.
ˆ A magnetic nucleus can take 2I+1 different orientations under the influence of an exter-
nal magnetic field. For example a proton with I=1/2 can take 2 × 21 +1=2 orientations
either aligned or opposed to the external magnetic field.

19. What is 1 H NMR spectroscopy?

The spectroscopic application based on the nuclear magnetic resonance of hydrogen nucleus
is called proton magnetic resonance spectroscopy (PMR spectroscopy or 1 H NMR spec-
troscopy).
20. Explain the theory of 1 H NMR spectroscopy
Since the hydrogen nucleus has a spin quantum number 21 , it can have 2 × 12 +1=2 orientations
when an external magnetic field is applied as shown in the figure.
ˆ Hydrogen nucleus is a spinning magnet
which has a mechanical spin and electric
charge associated with it.
− 21 Spin state ˆ When an external magnetic field is ap-
plied, the nucleus begins to wobble or
precess (like a spinning top does due
to the influence of earth’s gravitational
energy

field) about its own axis of spin with an

∆E
angular frequency (ω). This frequency
is called precessing frequency or Larmor
frequency.

ˆ Since the nucleus has charge, the pre-

+ 21 Spin state cession generates an oscillating electric
field of same frequency. If radio wave
no field applied magnetic field of the same frequency is supplied to the
precessing proton the energy can be ab-
sorbed, causing a spin change. This is
called nuclear magnetic resonance.
ˆ The energy absorbed ∆E from the radiation,
∆E = E− 1 Spinstate − E+ 1 Spinstate
2 2

ˆ It is also known that the energy difference is a function of applied magnetic field (B0 )
∆E = f (B 0 )

ˆ The magnitude of energy separation also depends on the particular nucleus involved.
Each nucleus has a different ratio of magnetic moment to angular momentum since each
has different charge and mass. This ratio is called magnetogyric ratio (γ) which is a
constant for each nucleus. For proton γ= 26.75×107 T−1 s−1 Therefore,
∆E = hν = f (B 0 )

ˆ Since the angular momentum is quantized in units of h

2π ,

h γ
∆E = hν = γ B0 or ν= B0
2π 2π

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Solved Numerical Problems

S5. Calculate the frequency at which radiations come into resonance with proton spins. The
magnetic fields applied are (a)1 T (b) 1.41 T (c) 12 T
Answer: (a) 42.6 MHz (b) 60 MHz (c) 511 MHz

21. How specroscopic analysis of compounds are done using NMR phenomenon?

ˆ The spectroscopic analysis is based on the fact that in a given molecule all the protons
do not resonate at the same frequency. This is due to the fact that protons in a molecule
are surrounded by electrons.
ˆ The electron density varies from one proton to another. In an applied magnetic field,
the valence electrons are caused to circulate creating a local diamagnetic current which
generates a magnetic field that opposes the applied magnetic field. This is called dia-
magnetic shielding.
ˆ As a result of diamagnetic shielding, each proton in a molecule is shielded from the
applied magnetic field to an extent that depends on the electron density surrounding
it. This means that protons with different electron density surrounding them absorbs
at slightly different frequencies.

But the difference in resonance frequencies is very small. In order

CH3 to overcome this difficulty, a reference compound, tetramethyl
silane (TMS) is placed in the solution of the substance to be
CH3 Si CH3 measured. The resonance frequency of each proton in the sample
is measured relative to the resonance frequency of the protons of
the reference compound. In other words the frequency difference
CH3
is measured directly.
22. Why tetramethyl silane (TMS) is used as the internal reference in NMR spec-
troscopy?
TMS is used as the internal reference universally owing to following reasons

ˆ TMS has 12 magnetically equivalent protons. So it gives a strong signal in NMR even
at low concentrations
ˆ TMS has a low boiling point (27◦ C) and can be easily recovered
ˆ It is soluble in organic solvents and is chemically very inert
ˆ Due to greater and powerful shielding effect electron density (owing to inductive (+I
effect of Si) TMS protons come to resonance at low frequency(defined as zero)

23. Explain the term chemical shift

ˆ The shift from TMS for a given proton depends on the strength of the applied magnetic
field.
ˆ In order to avoid this and help comparison of data taken using different strength of
magnetic field, a new parameter that is independent of field strength is defined. This is
called chemical shift (δ).
ˆ It is expresses the amount by which a proton resonates is shifted from TMS, in parts
per million (ppm) of the spectrometer’s basic operating frequency.

νSample − νT M S
δ= × 106
ν0

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ˆ Where νSample is the absorption frequency of protons of the sample νT M S is the absorp-
tion frequency of protons of TMS ν0 is the operating frequency of NMR instrument

24. Explain shielding and deshielding

ˆ If the induced magnetic field opposes the applied field, the net field experienced by a
proton will be less than the applied filed and the proton is said to be shielded. Be-
cause the proton experiences lower magnetic field, it needs a lower frequency to achieve
resonance, and therefore, shows lower chemical shift.
ˆ If the induced magnetic field reinforces the applied field, the net field experienced by
a proton will be higher than the applied filed and the proton is said to be deshielded.
Because the proton experiences higher magnetic field, it needs a higher frequency to
achieve resonance, and therefore, shows higher chemical shift.

25. Explain spin-spin splitting in NMR sprctra

ˆ The signals in NMR spectra are splitted by spin-spin coupling. It arises due to coupling
interaction between neighbouring protons.

X C C Y ˆ Consider two nearby protons HA and HB in the following

compound. They are in different magnetic environment. So
HA HB they resonate at different frequencies.
ˆ The resonance frequency of proton HA depends on its total magnetic environment.The
neighbouring proton HB itself is a magnet and can have its magnetic field either aligned
with the magnetic field of HA or opposed to it.
ˆ So the proton HB either decreases the net magnetic field experienced by HA or increases
it.
HA HB
ˆ In a given sample there are approximately equal
numbers of shielded and deshielded HA protons. This
causes HA protons to resonate at two different fre-
quencies.
ˆ The difference is very small therefore instead of two
Intensity

sharper peaks, HA gives a doublet.

ˆ A similar type of magnetic influence will be there
on HB proton by HA proton. So HB also gives a
doublet. The recorded NMR will be as shown in the
figure. Both the frequencies of the doublet will be of
Chemical shift (δ) the same intensity.

ˆ If the number of neighbouring protons for a group of protons is n, then the protons will
give n+1 signals. i.e. multiplicity =n+1. This is called n+1 rule. The intensity ratios
of multiplets can be found from Pascal’s triangle given below.
m = 1(Singlet) 1
m = 2(Doublet) 1 1
m = 3(T riplet) 1 2 1
m = 4(Quartet) 1 3 3 1
m = 5(Quintet) 1 4 6 4 1
m = 6(Sextet) 1 5 10 10 5 1
m = 7(Septet) 1 6 15 20 15 6 1

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26. What are the factors affecting chemical shift?

(a) Electronegativity
Electronegativity of substituents:-In compounds of the type CH3 – X, as X becomes
more electronegative, the chemical shift value of CH3 protons increases. The reason
is that when electronegativity of X increases the shielding effect experienced byCH3
protons decreases (deshielding)
Compound CH3 F CH3 OCH3 (CH3 )3 N CH3 – CH3
Chemical shift 4.3 3.2 2.2 0.9
of CH3 protons

Compound CH3 – F CH3 – Cl CH3 – Br CH3 – I

Chemical shift 4.3 3.1 2.7 2.2
of CH3 protons

Cumulative effect of electronegative substituents:- More number of electronega-

tive atoms causes more deshielding and causes increased value for chemical shift
Compound CH3 – Cl CH2 Cl2 CHCl3
Chemical shift of CH3 pro- 3.1 5.3 7.3
tons
Distance from electronegative atom:- As the distance from electronegative atom
increases, the deshielding decreases and chemical shift decreases.
CH3 – CH2 – CH2 – Cl
1.0 2.0 3.0
(b) Magnetic anisotropy
ˆ In aromatic compounds such as benzene, the π-electrons generate a ring current
which will produce a magnetic field as shown in the figure. The position of the
protons makes them highly deshielded, which leads to their higher chemical shifts
(6.5-8 ppm).
ˆ Diamagnetic anisotropy is also responsible for the higher chemical shifts of vinylic
protons and aldehyde protons (4.5-6.5 ppm and 9-10 ppm, respectively). The π-
electrons circulate in such a way as to generate a magnetic field that reinforces the
external magnetic field in the regions of space occupied by the protons.

ˆ But in acetylene, diamagnetic anisotropy leads to lower chemical shifts (3 ppm).

The π-electrons circulate in such a way as to generate a magnetic field that opposes
the external magnetic field in the regions of space occupied by the protons.

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27. What are the applications of NMR spectroscopy?

(a) Structural elucidation of compounds:-

The number of main signals indicates the number of equivalent protons in a compound.
Their chemical shift values indicates what type of protons are present. Spin-spin splitting
indicates the number of neighbouring protons thereby the possible arrangement of groups
in a molecules.
(b) In qualitative analysis:-
NMR spectroscopy helps to determine the molar ratio of components in a mixture
(c) To study hydrogen bonds in a molecule
(d) To study keto-enol tautomerism
(e) It is used in MRI (Magnetic Resonance Imaging)

28. Predict the 1 H NMR spectrum of CH3 – CH2 – Cl

Answer:
Main signals
Number of main signals = Number of types of protons
= 2 (−CH3 signal and−CH2 signal)
Relative intensities of main signals = 3 : 2
Relative position of signals = δ(−CH3 ) < δ(−CH2 )
Splitting of – CH3 signal:-
Multiplicity = n + 1
=2+1
= 3(triplet)
Relative intensities of splitting = 1 : 2 : 1
Splitting of – CH2 signal:-
Multiplicity = n + 1
=3+1
= 4(quartet)
Relative intensities of splitting = 1 : 3 : 3 : 1

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29. Write a note on magnetic resonance imaging (MRI)

ˆ MRI is a medical imaging technique used in radiology to visualize internal structure of

the body in detail. MRI makes use of nuclear magnetic resonance to image nuclei of
atoms inside the body
ˆ Living tissue is rich in protons, mainly from water. When the tissue is placed inside a
powerful magnetic field ( 1.5 T), the magnetic moment of protons gets aligned with the
direction of the field.
ˆ Then a radio frequency is briefly turned on, producing radio waves resonance frequency.
The radio waves are absorbed by the protons and the spin states are changed.
ˆ Once the RF signal is turned off, the magnetic moments realign by emitting radio waves.
This signal is called free induction decay (FID) response signal. This is measured by a
conductive coil placed around the tissue and reconstructed to obtain a density map or
image.
ˆ To produce a 3D image a gradient magnetic field is used. This gradient field causes the
resonance frequency to change linearly in the direction of the field.
ˆ By repeating the process across several slices of the tissue a complete reconstructed
image is produced. Therefore MRI is called tomography (tomos means slices) or zeug-
matography (zeugma means to join)

Solved Spectral Problems

Cl
S6. Predict the 1 H NMR spectrum of CH3 CH Cl
Answer:

Cl
S7. Predict the 1H NMR spectrum of CH3 CH CH3
Answer:

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Kozhummal R., Engg. Chemistry

S8. Predict the 1 H NMR spectrum of CH3 – CH2 – CH2 – Cl

Answer:

O
S9. Predict the 1 H NMR spectrum of CH3 CH2 C O CH3
Answer:

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KTU Examination Questions

K4.1. 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 (Jan 2016, 4 Marks)
K4.2. What is chemical shift? Write the cause of chemical shift (Jan 2016, 4 Marks)
K4.3. Which of the following nuclei can give NMR spectrum? Give reason a) 11H b) 12
6C c)
19
9F d) 168O (May/June 2016, 2 Marks)
K4.4. How can you distinguish NMR spectrum of CH3 CH2 Cl and CH3 CHCl2 applying the
concept of spin-spin splitting? (May/June 2016, 3 Marks)
K4.5. Predict NMR spectrum of CH3 – CHCl – CH3 (May/June 2016, 3 Marks)
K4.6. What is spin-spin splitting? Write the splitting pattern in the NMR spectrum of
CH2 ClCH2 CH2 Cl (July 2016, 3 Marks)
K4.7. Explain the principle of NMR spectroscopy. Which of the following nuclei can have a
presence in NMR spectrum? (i) 168O (ii) 136C (iii) 21H Reason for your answer (July
2016, 4 Marks)
K4.8. Define chemical shift. Interpret the number of signals, the position of signals and the
intensity of signals in the NMR spectrum of CH3 CH2 CH2 Cl (July 2016, 4 Marks)
K4.9. Why is TMS taken as reference to determine chemical shift value in NMR spectroscopy?
(Aug 2016, 3 Marks)
K4.10. What is meant by the term shielding in NMR spectroscopy? Arrange the CH3 F, CH3 Cl,
CH3 Br and CH3 I in the increasing order of shielding effect. Give the reason for your
answer. (Aug 2016, 3 Marks)
K4.11. Give the reason for high δ-value of aromatic protons. (Aug 2016, 4 Marks)
K4.12. 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 (Aug 2016, 4 Marks)
K4.13. What is MRI? How is it useful in the field of medicine? (Aug 2016, 3 Marks)
K4.14. Explain spin-spin splitting. Write the splitting pattern in the NMR spectrum of
CH2 Cl – CH2 – CH2 Cl (Jan 2017, 4 Marks)
K4.15. What is chemical shift/ explain Shielding and Deshielding (Jan 2017, 6 Marks)
K4.16. Predict the splitting pattern in the NMR spectra of CH3 CH2 COOCH3 and CH3 CHCl2 .
Briefly explain chemical shift and factors affecting it. (May 2017, 5 Marks)
K4.17. Chemical shift value of methyl chloride is lower compared to that of methyl fluoride.
Why? (May 2017, 2 Marks)
K4.18. Briefly explain chemical shift and factors affecting it (May 2017, 5 Marks)
K4.19. Which of the following nuclei do not show NMR spectrum? Why? a) 11H b) 12
6C c)
19
9F d) 168O e) 147N (July 2017, 2 Marks)
K4.20. Predict the number of signals in NMR spectrum of the following compounds i) cyclobu-
tane ii) 1,2-dichloroethane iii) 2-chloropropane iv) vinyl chloride (July 2017, 4 Marks)
K4.21. Draw the structure of the following compounds satisfying the given NMR spectral data
i) C3 H7 Cl- one doublet (6H) and one septet (1H)
ii) C4 H10 O- one singlet (3H) and one doublet (6H) and one septet (1H) (July 2017, 6
Marks)
K4.22. How will you distinguish ethanol and dimethyl ether using NMR specroscopy? (Dec
2017, 5 Marks)

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Kozhummal R., Engg. Chemistry

K4.23. Define chemical shift in NMR spectroscopy. Also explain the factors influencing chemical
shift. (Dec 2017, 5 Marks)
K4.24. How many signals are observed on the 1H NMR spectrum of Cl – CH2 – CH2 – Cl? Sub-
statiate your answer. (Apr 2018, 2 Marks)
K4.25. Explain spin-spin splitting. Write the splitting pattern in the 1HNMR spectrum of
ethanol. (Apr 2018, 6 Marks)

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