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STUDY MATERIAL
ENGINEERING CHEMISTRY (BBS00010)

Table of Contents

MODULE II: SPECTROSCOPIC TECHNIQUES AND APPLICATIONS

● Principles of spectroscopy and selection rule.

● Electronic spectroscopy of diatomic molecules and applications.
● Fluorescence and its applications in medicine.
● Vibrational spectroscopy of diatomic molecules. Applications.
● Basic idea on nuclear magnetic resonance.

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SPECTROSCOPY
It is the branch of science that deals (measures and interprets) with the electromagnetic spectra that
result from the interaction of electromagnetic radiation with matter as a function of wavelength or
frequency of radiation. It was first observed by Sir Isaac Newton while observing the splitting of light by a
prism, and he named it ‘Optics’.

Maxwell’s theory of electromagnetic radiation

● Electromagnetic radiation travels in the form of waves.
● Consists of both electric and magnetic fields.
● Oscillate in mutually perpendicular planes and perpendicular to the direction of propagation of the
wave.

Wave Number: The Reciprocal of wavelength.

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A few concepts about spectroscopy

● Absorption or emission of energy occurs in discrete energy packets.

ℎ𝑐
𝐸 = ℎ𝜈 =
𝜆
● Electromagnetic radiations can be arranged in increasing order of wavelength as shown below:

Cosmic ray < γ-ray < X-ray < UV < Visible < IR < Microwave < Radio wave

Decreasing frequency / increasing wavelength

Basic idea about the energy of a molecule

● Total energy of a molecule = Translational energy + Internal energy = Translational energy + (electronic
energy + vibrational energy + rotational energy + nuclear energy).

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● Translational energy is a function of temperature, so it is not considered in spectroscopy.

● When electromagnetic radiation falls on a molecule then the molecule absorbs energy from the radiation
and becomes excited to a higher energy state from a lower energy state.

Spectroscopy can be generally classified into two types, viz., Absorption spectroscopy and
Emission spectroscopy. The absorption spectroscopy is formed by the frequencies of light transmitted with
dark bands when energy is absorbed by the electrons in the ground state to reach higher energy states. In
contrast, emission spectroscopy is formed by the frequencies of the emitted light when electrons radiate
energy to return to the ground state from higher excited states.

ELECTRONIC (UV-VIS) SPECTROSCOPY

● Absorption of radiation in the ultraviolet and visible region causes promotion of electrons from lower
energy σ, π and n molecular orbitals to vacant higher energy π* and σ* molecular orbitals.
● It is interpreted simply by a plot of wavelength λ (nm) of light absorbed versus the absorption intensity.

● 𝜆𝑚𝑎𝑥 : When molar absorptivity is plotted against wavelength, then absorbance becomes maximum at

a particular wavelength known as 𝜆𝑚𝑎𝑥 . Every compound has distinct 𝜆𝑚𝑎𝑥 value.

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UV-Vis Spectrophotometer

● Source of Light in UV Region: Hydrogen or deuterium discharge lamp.

● The cell used is the quartz cell of dimensions 1 cm x 1 cm.

● Choice of Solvent:
i. Should have high purity.
ii. Must not absorb radiation itself.
iii. Must be chemically inert to the sample.
● Commonly used Solvents: n-hexane, 95% ethanol, water, etc.

Basic principle of UV-Vis spectroscopy

The UV-Vis spectroscopy is based on Lambert-Beer’s Law. Lambert-Beer’s law states that the
absorbance (A) of monochromatic light is directly proportional to the path length (l) and concentration of
solution (c).
Consider a UV or visible radiation with intensity I0 incident on a liquid sample with concentration
c and path length l. The sample absorbs the UV radiation, and the intensity of the transmitted light is I.

𝐼0
Lamber-Beer’s Law: 𝑙𝑜𝑔 =𝐴 (A = Absorbance)
𝐼
Thus, A = ξcl (ξ = Molar absorptivity/extinction coefficient)
ξ = A/cl (c = concentration of solution; l = path length)
𝐼
and, =𝑇 (T = Transmittance)
𝐼0

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Lambert-Beer’s law is the combination of two different and independent laws, viz., Lambert's law
and Beer's law.

Lambert law
It states that the rate of decrease in intensity of the incident light is directly proportional to the path
length, i.e., the distance travelled by the UV/Visible radiation through the sample.
Mathematically,
𝑑𝐼
− ∝𝑙 … . . (𝑖)
𝐼
Integration of this, we get
ln (I/I0) = – Kl + C [C is integration const.]
When l = 0, I = I0, so we will get
ln (I0/I) = Kl
Or, I = I0 e-Kl

Beer law
It states that the rate of decrease in intensity of the incident light is directly proportional to the
concentration of the sample.
Mathematically,
𝑑𝐼
− ∝𝑐 … . . (𝑖𝑖)
𝐼
Integration of this, we get
ln (I/I0) = – Kc + C [C is integration const.]
When l = 0, I = I0, so we will get
ln (I0/I) = Kc
Or, I = I0e-Kc

Derivation of Lambert-Beer’s law

Combining equations (i) and (ii) we get
𝑑𝐼 𝑑𝐼
− ∝ 𝑙. 𝑐 ⇒ − = 𝐾. 𝑙. 𝑐
𝐼 𝐼

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Integrating the above equation with limits I0 and I, we get

𝐼
𝑙𝑛 𝑙𝑛 = −𝐾. 𝑙. 𝑐
𝐼0
𝐼0
𝑜𝑟, 𝑙𝑛 𝑙𝑛 = 𝐾. 𝑙. 𝑐
𝐼
𝐼0
𝑜𝑟, 2.303 𝑙𝑜𝑔 𝑙𝑜𝑔 = 𝐾. 𝑙. 𝑐
𝐼
𝐼0 𝐾
𝑜𝑟, 𝑙𝑜𝑔 𝑙𝑜𝑔 = . 𝑙. 𝑐
𝐼 2.303
𝐼0
𝑜𝑟, 𝑙𝑜𝑔 𝑙𝑜𝑔 = 𝜖. 𝑙. 𝑐
𝐼
𝑜𝑟, 𝐴 = 𝜖. 𝑙. 𝑐

𝐼0
Where A is the absorbance or optical density (A = 𝑙𝑜𝑔 𝑙𝑜𝑔 𝐼
) and 𝜖 is the molar absorptivity
coefficient or molar extinction coefficient.

NOTE:
𝐼
𝐴 = − 𝑙𝑜𝑔 𝑙𝑜𝑔 𝑇 ⇒ 𝑇= = 10−𝐴
𝐼0

Electronic transitions in molecular orbitals

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Probability of transition concerning energy gaps/number of transitions

σ to σ* < n to σ*< π to π* < n to π*

● Allowed transition: σ 🡪 σ* and π 🡪 π* transitions.

● Forbidden transition: n 🡪 π * and n 🡪 σ * transitions.

Chromophore
The presence of an isolated functional group which is not in conjugation with any other group is
said to be called a chromophore. They show characteristic absorption in UV-Vis spectra and thus, reflect
characteristic colour.
A few examples are given below:

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Auxochrome
These are groups of atoms which can alter the capacity of the chromophore to reflect colours. They
impart a particular colour when attached to a chromophore, but when present alone, they will fail to produce
that colour. When attached to a chromophore, they interact with it and cause a shift in the absorption,
towards longer or shorter wavelengths.
A few examples are given below:

BATHOCHROMIC SHIFT (RED SHIFT)

● Shift of absorption maxima towards higher wavelengths (Lower energy).
● Example: When phenol is treated with alkali, then phenoxide ion is produced, and n to π* transition
increases due to the increase in conjugation. So, the absorption maxima also increase and shift towards
higher wavelengths. The higher wavelength indicates red colour, thus known as the Red shift.

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HYPSOCHROMIC SHIFT (BLUE SHIFT)

● Shift of absorption maxima towards lower wavelengths (higher energy).
● Example: When aniline is converted to anilinium ion, then nitrogen lone pair electrons are not available
for delocalisation and thus, n to π* transition decreases. So, the absorption maxima also decrease and
shift towards a lower wavelength.

Effect of conjugation in polyenes on λmax

The greater the conjugation, the lower will be the energy difference between π and π* orbitals, and
the higher will be the π and π* transitions. Thus, π to π* transition shifts towards higher wavelength, and
the λmax will be greater. Example: 1, 3-butadiene absorbs at a higher wavelength than ethylene.

● 1, 3-butadiene can exist in two configurations: s-cis and s-trans.

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In s-cis butadiene, two H atoms are on the same side of the double bond; thus, there exists a strong
repulsion between them. So, the energy gap of π 🡪 π* increases and the number of transitions decreases;
hence, λmax shifts towards a lower wavelength.
The case will be opposite for s-trans configuration. The more stable s-trans 1, 3-butadiene absorbs
at longer wavelength than s-cis 1, 3-butadiene and has higher λmax value.

Steric effect
In the case of cis-stilbene, the two phenyl groups are on the same side, resulting in strong steric repulsion
between them, which decreases effective delocalisation. As a result, the energy gap of π → π increases, the
number of transitions decreases, and the λmax shifts towards a lower wavelength.

In the case of trans-stilbene, the two phenyl (-Ph) groups are on opposite sides. As a result, the
energy gap of π → π decreases, and the number of transitions increases due to higher stability.
Consequently, the λmax shifts towards a higher wavelength. Therefore, trans-stilbene absorbs at a longer
wavelength than cis-stilbene and has a higher λmax value.

Cis-Stilbene Trans-Stilbene

Applications of UV-Vis Spectroscopy

• In the polymer industry, UV-Vis spectroscopy is used to detect cross-links, flaws, and the kinetics
of polymeric chains.

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• In the pharmaceutical industry, it is used to identify both known and unknown medicinal
compounds.

Fluorescence

• When an electron returns from an excited electronic state to the ground state, it releases the
absorbed energy in the form of light and heat.

• The instantaneous emission of a portion of the absorbed energy by certain substances is referred to
as luminescence, which can be categorized into fluorescence and phosphorescence.

• Fluorescence occurs within a few nanoseconds (10⁻⁸ to 10⁻⁹ seconds) after the excitation of the
molecule by absorbing energy from a light source (such as a UV lamp).

• Quinine, the first known fluorophore, stimulated the development of the first spectrofluorometer.

• Generally, aromatic molecules exhibit fluorescence. Some common fluorescent substances

include:

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Principle of Fluorescence
Fluorescence is the process occurring between absorption and emission of light by a fluorescent
substance, which is best explained by the Jablonski diagram.

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JABLONSKI Diagram

• The Jablonski diagram is used to illustrate the absorption and emission of light during various
molecular processes that occur in the excited state.

• The absorption of radiation promotes the molecule from the ground state to a singlet excited state (S₁,
S₂, S₃, etc.).

• As the excited molecule collides with surrounding molecules, it releases some energy through
radiationless transitions (non-radiative decay) such as vibrational relaxation, internal conversion, or
intersystem crossing.

• The transition of a molecule from the lowest vibrational level of the first singlet excited state (S₁) to the
ground state (S₀) is called fluorescence (a type of radiative decay).

• The part of the molecule responsible for fluorescence is called a fluorophore.

• The spectral data of fluorescent substances are typically presented as emission spectra, which
represent a graph of fluorescence intensity versus wavenumber (cm⁻¹).

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Instrumentation of Fluorescence Spectroscopy

An instrument used for fluorescence has five essential components, which are as follows:
i. A light source, which will provide radiation for excitation.
ii. A monochromator to select the wavelength of the radiation for excitation.
iii. A sample cell.
iv. An emission monochromator for analyzing the emitted light.
v. A photosensor to measure the intensity of the emitted light.

The schematic diagram of the instrumentation used to perform the fluorescence spectroscopy is as
follows:

Applications of Fluorescence in Medicine

● Systematic studies of fluorescence decay characteristics/lifetime contrast is used in diseased tissue
characterizations and diagnosis.
● Fluorescence helps analyze the concentration of Riboflavin (Vitamin B2) in chloroform.

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● Laser-induced fluorescence (LIF) spectroscopy of tissues in the human body is used for the diagnosis
of tumors or cancer.
● Fluorescence spectroscopy is also widely used in the accurate determination of an anomalous amount
of glucose.
● Time-resolved fluorescence or autofluorescence techniques are applied in the detection of eye diseases.

VIBRATIONAL (IR) SPECTROSCOPY

● The IR radiation interacts with matter at the molecular level. It tends to vibrate the molecules along
their axes and planes. Thus, IR spectroscopy is also called ‘Vibrational Spectroscopy’.
● Range of IR spectrum: 750 nm to 1 mm (wavelength), 430 THz to 700 GHz (frequency), 400 cm -1 to
4000 cm-1 (wave number), 1.7 eV to 1.24 MeV (photon energy).

Principles of IR spectroscopy
i. Every molecule has an intrinsic frequency of vibration according to its specific bonds and functional
groups present in it.
ii. IR radiation tends to vibrate the bonds between the atoms of the molecules with characteristic
frequencies.
iii. The absorption of IR radiation occurs only when the natural frequency of vibration and the
frequency of the IR radiation match. Hence, resonance occurs, and atoms of the molecules and the
bonds between them vibrate more vigorously.
iv. If the absorption of IR radiation causes a change in the dipole moment of a molecule, it is said to be
IR-active. If there is no change in dipole moment, the molecule is considered IR-inactive..

Types of vibrations
i. Stretching (along the molecular axes):
a. Symmetric stretching.
b. Anti-symmetric stretching.

ii. Bending (along the molecular planes):

a. In-plane bending – Scissoring and Rocking.

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b. Out-of-plane bending – Wagging and Twisting.

Symmetric & Antisymmetric stretching

Carbon dioxide (CO2) is heteronuclear triatomic linear molecule. The different vibrational modes
of CO2 are shown here.

Symmetric stretching Antisymmetric stretching

Carbon dioxide molecule

Bending
It always happens along planes. (a) in-plane bending, viz., scissoring and rocking; and (b) out-of-
plane bending, viz., wagging and twisting.

Bending mode of CO2:

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IR-Inactive and IR-Active Molecules

i. Homonuclear diatomic molecules:

These molecules always have an intrinsic dipole moment of zero. Therefore, upon stretching or
compressing, there is no change in their dipole moment. Hence, homonuclear diatomic molecules are
always IR-inactive.
Examples: O₂, H₂, N₂, F₂, Cl₂, Br₂, I₂.

ii. Heteronuclear diatomic molecules:

These molecules always have a non-zero intrinsic dipole moment, which persists upon stretching or
compressing. Therefore, heteronuclear diatomic molecules are always IR-active.
Examples: HF, HCl, HBr, HI, CO, NO.

iii. Heteronuclear triatomic linear molecules:

• Some of these molecules have an intrinsic dipole moment of zero. Thus, during symmetric
stretching, there is no change in dipole moment, and they are IR-inactive in such cases.
Examples: CO₂, CS₂, XeF₂, BeCl₂.
• However, these same molecules exhibit a change in dipole moment from zero to non-zero during
antisymmetric stretching or bending. Hence, they are IR-active in those modes.
• Some heteronuclear triatomic linear molecules, such as O=C=S and HCN, always have a non-zero
intrinsic dipole moment. Therefore, they are IR-active during all types of vibrational motion,
including stretching, compressing, and bending.

iv. Homonuclear triatomic non-linear molecules (e.g., O₃⁻, S₃) and heteronuclear triatomic non-
linear molecules (e.g., H₂O, H₂S):
These molecules always have a non-zero intrinsic dipole moment and are therefore IR-active in all
vibrational modes—symmetric/antisymmetric stretching, compressing, and bending.

v. Polyatomic molecules (e.g., tetratomic molecules such as NH₃, CH₄, CCl₄, CHCl₃, CH₃Cl):
These molecules are generally IR-active in all cases of symmetric/antisymmetric stretching, compressing,
and bending due to the presence of polar bonds and changes in dipole moment during vibration.

SUMMARY

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Dipole moment Dipole moment

Type of the Name of the Type of before IR after IR
Result
molecule molecule vibration radiation radiation
adsorption absorption

Homonuclear Symmetric IR-inactive

O2, H2, N2, μ=0 μ=0
diatomic stretching always
F2, Cl2, Br2,

molecules I2, etc. Doesn’t exhibit Antisymmetric stretching or Bending

HF, HCl, Symmetric IR-active

Heteronuclear μ1 ≠ 0 μ2 ≠ 0
HBr, HI, stretching always
diatomic
CO, NO,
molecules Doesn’t exhibit Antisymmetric stretching or Bending
etc.

Symmetric
μ=0 μ=0 IR-inactive
CO2, CS2, stretching

XeF2, Antisymmetric
Heteronuclear μ=0 μ=0
BeCl2, etc. stretching and IR-active
triatomic (Both cases) (Both cases)
Bending
linear
molecules Symmetric and
O=C=S, Antisymmetric μ1 ≠ 0 μ2 ≠ 0 IR-active
HCN, etc. stretching, (All cases) (All cases) always
Bending

Heteronuclear Symmetric and

H2O, H2S,
triatomic non- Antisymmetric μ1 ≠ 0 μ2 ≠ 0 IR-active
etc.
linear stretching, (All cases) (All cases) always
molecules Bending

Number of vibrational modes

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A molecule can vibrate in many ways, and each way is called a vibrational mode (also called a
vibrational degree of freedom). For molecules with N number of atoms, geometrically linear molecules
have 3N–5 degrees of vibrational modes, whereas non-linear molecules have 3N–6 degrees of
vibrational modes. Example: Linear carbon dioxide (CO2) has 3 × 3 – 5 = 4, while non-linear water (H2O)
has only 3 × 3 – 6 = 3.

Problem: Find the vibrational degrees of freedom of the CO2 and H2O molecules. Find out the
number of IR-active and IR-inactive vibrations for each.

Answer: According to the theory, the number of vibrational degrees of freedom for linear molecules
is (3N – 5) and for non-linear molecules is (3N – 6). Here, CO2 is a linear molecule and H2O is a non-linear
molecule. Thus,
The number of vibrational degrees of freedom of CO2 is (3 × 3 – 5) = 4, and
The number of vibrational degrees of freedom of H2O is (3 × 3 – 6) = 3
Also, linear molecules always undergo one symmetric stretching vibration, which is an IR-inactive
vibration and the rest are IR-active. So, for CO2, among these 4 vibrational degrees of freedom, 1 is IR-
inactive (symmetric stretching) and 3 are IR-active (1 anti-symmetric stretching and 2 bending).
Similarly, non-linear molecules undergo all types of stretching and bending and are IR-active. Thus,
for H2O, among these 3 vibrational degrees of freedom, all are IR-active (1 symmetric stretching, 1
anti-symmetric stretching, and 1 bending).

IR Stretching Frequency
● Depends directly on force constant (strength of bonding between the two atoms, i.e., (ν ~ k).
● Depends inversely on the reduced mass of the two atoms, i.e., (ν ~ 1/μ).
1 𝑘
● IR stretching frequency (ν): 𝜈 = √
2𝜋 𝜇 (in Hz), and,

1 𝑘
● Wavenumber (𝜗): 𝜗= √ (in cm-1)
2𝜋𝑐 𝜇
Where, 𝜈 = Frequency of vibration (Hz), k = Force constant (N/m), and μ =
reduced mass (kg).

𝑚 𝑚
● Reduced mass, 𝜇 = 𝑚 𝐴+ 𝑚𝐵 where 𝑚𝐴 and 𝑚𝐵 are the masses of two different atoms.
𝐴 𝐵

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Problem: Find the fundamental IR stretching frequency and wavenumber of the HCl molecule.
Given kHCl = 475.6 N/m.
1 𝑘
Answer: According to the formula, 𝜈 = √
2𝜋 𝜇

Now, for HCl molecule, kHCl = 475.6 N/m = 475.6 kg/s2, and
𝑚𝐻 × 𝑚𝐶𝑙
𝜇𝐻𝐶𝑙 = × 𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑢𝑛𝑖𝑡
𝑚𝐻 + 𝑚𝐶𝑙
1 × 35.5
= × 1.66 × 10−27 𝑘𝑔
1 + 35.5
= 1.61 × 10−27 𝑘𝑔

So, the fundamental IR stretching frequency will be,

1 𝑘
𝜈= √
2𝜋 𝜇

1 475.6 𝑘𝑔/𝑠 2
= √
2 × 3.14 1.61 × 10−27 𝑘𝑔

= 0.8654 × 1014 𝑠 −1
= 8.654 × 1013 𝑠 −1

1 𝑘
Again, 𝜗= √
2𝜋𝑐 𝜇
= 𝜈𝑐
Thus, wavenumber
8.654 × 1013 𝑠−1
𝜗=
3.8 × 1010 𝑐𝑚 𝑠−1
= 2.28 × 103 𝑐𝑚−1
Hence, the IR stretching frequency of the HCl molecule is 8.654 × 1013 s-1 and that of wavenumber
is 2.28 × 103 cm-1.

Energy of vibration
From the Schrödinger equation, we get the value of vibrational energy:

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1
𝐸𝑣𝑖𝑏 = (𝑣 + ) ℎ𝜈𝑜𝑠𝑐 (in Joule)
2
1
𝑜𝑟, 𝜀𝑣𝑖𝑏 = (𝑣 + ) 𝜗𝑜𝑠𝑐 (in cm-1)
2

Selection rule
From the Schrödinger equation, we get that the allowed transitions for vibrational energy levels is
∆𝑣 = ±1, where +1 is for absorption of vibrational energy and –1 is for emission of vibrational energy.
(𝑣) It is the vibrational quantum number.

Zero-point energy
The value of 𝒗 (vibrational quantum number) can start from 0. Thus, putting 𝒗 = 0, we get
1
vibrational energy 𝜀𝑣𝑖𝑏 = 𝜗𝑜𝑠𝑐 cm-1. Thus, even if the molecule is at rest (i.e., 𝒗 = 0), the vibrational
2
1
energy of the system is not exactly zero. It has a minimum value of 𝜗 cm-1, and this is known as
2 𝑜𝑠𝑐
‘Zero-point energy’. Thus, molecules are never at complete rest concerning each other.

Problem: Find the energy of vibration for the third vibrational level of a system with 𝜗𝑜𝑠𝑐 =

18770 𝑐𝑚−1
Answer: At the third vibration level, (𝑣 = 3),
1
𝜀𝑣𝑖𝑏 = (3 + )𝜗
2 𝑜𝑠𝑐

1
= (3 + ) × 18770 𝑐𝑚−1
2
7
= × 18770 𝑐𝑚−1
2
= 65695 𝑐𝑚−1 (𝑎𝑛𝑠𝑤𝑒𝑟)

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Problem: Examine which one between H3C−CH3 and H2C=CH2 will have higher IR
stretching frequency of the C−C bond. Explain your answer.

Answer: According to the formula, the IR stretching frequency of any molecule is directly
proportional to the force constant of the given molecule. The force constant is, in turn, directly proportional
to the bond strength of the molecule. We know that the increasing order of the bond strength is given by
Triple bond > Double bond > Single bond
Here, the two given molecules are H3C–CH3 (ethane) and H2C=CH2 (ethene); ethane has C–C single
bond while ethene has a C=C double bond. According to the order of bond strength, ethane has a higher
force constant than ethane. Thus, between H3C–CH3 and H2C=CH2, H2C=CH2 has a higher stretching
frequency of C–C bond.

Problem: Select the compound with the higher IR stretching frequency. Explain the reason.
i. Propanal and Propanone.
ii. 2-Butanone and But-3-en-2-one.

Answer: The stretching frequency of the above compounds depends on the bond strength of the
carbonyl group (>C=O).
i. Between propanal and propanone, propanal has a higher IR stretching frequency.
In propanal, the functional group is an aldehyde, and in propanone, the functional group
is a ketone. In ketones, the presence of more +I effect due to the presence of two alkyl
groups lowers the C=O bond strength, while in aldehydes, there is less +I effect due
presence of one hydrogen and one alkyl group. Thus, aldehyde, i.e., propanal, has a
higher IR stretching frequency than ketone, i.e., propanone.

ii. The structures of the two compounds are given below:

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In but-3-en-2-one, the C=C double bond is in conjugation is C=O group, hence the C=O
bond assumes a single bond character and the bond strength decreases, while in 2-
butanone, there is no double bond conjugation and the bond strength remains the same.
Hence, 2-butanone has a higher IR stretching frequency than but-3-en-2-one.

Applications of IR Spectroscopy

i. Different molecules absorb IR radiation at characteristic frequencies based on their specific bonds and
functional groups. As a result, they exhibit distinctive peaks in the IR spectrum. Therefore, the IR
spectrum of a molecule serves as the “fingerprint” of that molecule. The fingerprint region in an IR
spectrum typically ranges from 1500 cm⁻¹ to 600 cm⁻¹.

ii. Like a fingerprint, no two molecules absorb identical IR frequencies. This uniqueness makes IR
spectroscopy a powerful tool for the identification and analysis of different compounds.

iii. It is widely used for structural determination and for the detection of impurities in various
substances.

iv. IR spectroscopy can distinguish between intermolecular and intramolecular hydrogen bonding.

v. It is also useful in the kinetic study of chemical reactions.

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Nuclear Magnetic Resonance (NMR) Spectroscopy

● It involves the interaction between oscillating electromagnetic radiation and the magnetic properties of
certain nuclei, notably the nucleus of the hydrogen atom- the proton.
● Examples of magnetic isotopes are 13C, 1H, 19F, 14N, 17O, 31P, etc.
● If a nucleus is not magnetic, it can’t be studied by NMR spectroscopy.
● NMR is based on the measurement of absorption of electromagnetic radiation in the radio frequency
region from roughly 4 to 900 MHz.
● The absorption of radio waves in the presence of a magnetic field is accompanied by a specific type of
nuclear transition. For this reason, this type of spectroscopy is known as nuclear magnetic resonance
(NMR) spectroscopy.
Nuclear spin

● Just as electrons spin about their axis, it is believed that the protons and neutrons present in the nuclei
of atoms also spin about their axes.
● The nuclear spin quantum number (I) for the nucleus can then have values 0, 1/2, 1, 3/2, 2, etc.,
depending upon the number of neutrons and protons having parallel and antiparallel spins. e.g.,
deuterium nucleus, which contains one proton and one neutron expected to have either I = 1 (for parallel
spin) or I = 0 (for antiparallel spin). The deuterium nucleus is found to have I = 1 in the ground state,
indicating that the proton and neutron have parallel spins.
● Table for nuclear spin quantum number (I)

Sl. No. Mass number Atomic number Nuclear spin (I) Examples

(i) Odd Odd or Even 1/2, 3/2, 5/2, … 1 19 23 35

1H , 9F , 11Na , 17Cl , etc.

4 12 16 32
(ii) Even Even 0 2He , 6C , 8O , 16S , etc.

(iii) Even Odd 1, 2, 3, … 2 10 14

1 D , 5B , 7N , etc.

● Since a nucleus possesses an electric charge, the spinning nucleus gives rise to a magnetic field whose
axis coincides with the axis of spin. Each nucleus with I = 0 does not possess a magnetic moment and
hence does not respond to NMR spectroscopy.

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Interpretation of the NMR Spectra

The recorded NMR of a substance gives the following information:

i. Number of peaks:
The number of signals in the spectrum indicates the various types of protons present in the
substance, e.g., if two peaks are observed in the NMR spectrum of a compound, then there are
two types of protons in the compound. It may be noted that magnetically equivalent protons are
chemically equivalent protons.

ii. Position of peaks (Chemical Shift):

The position of the peaks indicates the electronic environment of each kind of proton, viz.,
aromatic, aliphatic, acetylenic, vinylic, adjacent to some electron-attracting or electron-releasing
groups, etc.
The circulating electrons in a molecule produce a secondary magnetic field (induced
magnetic field) which generally tends to oppose the applied field on the proton itself. Thus, the
field felt by the proton is diminished, and the proton is said to be shielded. But if the induced
field reinforces the applied field, the proton feels a higher field strength and thus such a proton
is said to be deshielded.
Shielding shifts the absorption upfield, and deshielding shifts the absorption downfield.
Such shifts in the positions of the NMR absorptions, which arise due to the shielding or
deshielding of protons by the electrons, are called chemical shifts.
For measuring chemical shifts of various protons in a molecule, the signal for
tetramethylsilane (TMS) is taken as a reference. The difference in the absorption position of
the proton concerning the TMS signal is called the chemical shift value (δ-value).

TMS is the most convenient reference and has the following characteristics:

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a. All the 12 protons present in it are chemically equivalent, i.e., they have the same
environment and hence give a single well-defined absorption peak in the NMR
spectrum.
b. The protons are highly shielded by their electrons from the external magnetic field so
that they show NMR at a very high external magnetic field strength as compared to
other protons.
c. It is chemically inert and miscible with almost all organic compounds.
d. Its boiling point is low (34°C), so that it evaporates off quickly and the sample
compound is easily recovered.

Chemical shift is given by the equation:

ν s − ν T MS
δ= 10 6 ppm (parts per million)
ν0

Where, ν 0 is the frequency of the instrument, ν s is the resonance frequency of the sample

and ν T MS is the resonance frequency of TMS.

Thus, the signal for extremely shielded TMS appears at the extreme right of the spectrum
with δ = 0 ppm. The greater the deshielding of protons, the larger will be the value of δ. For most
of the organic compounds, signals appear downfield to the left of the TMS signal.

δ-scale for chemical shifts

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NMR spectrum of Ethyl bromide

iii. Splitting of Signals in the form of multiplets:

The splitting of the signals indicates the number of protons on the neighbouring carbon.
Multiplicity of signal is given by the (2nI + 1) rule, where n = number of protons on adjacent
carbon atoms and I = spin quantum number, which is 1/2 for a proton, so the effective formula
becomes (n + 1). The splitting of the NMR signal occurs due to spin-spin coupling.

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The 1H-NMR spectrum of ethanol (example given above) shows that the methyl peak has
been split into three distinct peaks (a triplet) and the methylene peak has been split into four
distinct peaks (a quartet). This occurs because there is a small interaction (spin-spin coupling)
between the two groups of protons.

It is important to remember that no splitting is caused in the following cases:

i. When all the protons in a molecule are equivalent. For example, in the case of
cyclobutane, benzene, etc., we observe a singlet.
ii. When a set of equivalent protons does not have another set of protons attached to the
adjacent carbon atom. For example, in the NMR spectrum of 2-butanone:
c b a

( C H 3 − C H 2 − CO − C H 3 )

A singlet appears for protons ‘a’, since there is no hydrogen atom attached to the
adjacent carbon atom. The hydroxyl proton also shows a singlet.

iv. Intensities of the Peaks:

The intensities (relative height) of the signal indicate the number of protons of each kind.
For example, if two signals are recorded on the NMR spectrum and the ratio of heights of the
signals is 3:2, then there are 3 protons of one type and 2 protons of the other type. The peak for
3 protons will show a doublet peak splitting, while the peak for 2 protons will show a triplet
peak splitting. The peak intensities of the various multiplets can be described by Pascal’s triangle
as follows:

Peak area ratio Peak splitting

1 Singlet
1:1 Duplet
1:2:1 Triplet
1:3:3:1 Quartet
1:4:6:4:1 Quintet
1:5:10:10:5:1 Sextet

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Applications of NMR spectroscopy

1. Determination of molecular structure and identity, monitoring reactions, and studying physical
properties at the molecular level.
2. Magnetic resonance imaging (MRI), which is based on the NMR technique, is used for diagnostic
purposes.

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