Ktu Engg Chemistry Notes

MODULE 1: SPECTROSCOPY AND ITS
APPLICATIONS
1. What is spectroscopy?
Spectroscopy is a branch of science deals with the study of the interaction between the
matter and electromagnetic radiation. It involves the production, measurement and
interpretation of electromagnetic spectra arising from emission or absorption of
electromagnetic radiations by atoms or molecules. It is the most powerful tool available for
the study of structures of atoms and molecules.
2. What are the advantages of spectroscopy?

• They require very less time for analysis.
• Less sample quantity is required.
• Sample materials remain unchanged during analysis and can be reused.
• They give accurate results.
3. What are the different types of spectra?
Based on the nature of interaction, the spectra can be divided as:

• 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 ℎ𝜈 , the spectrum
obtained is called an absorption spectrum. Microwave and NMR belongs to
absorption spectra.
• Emission Spectrum
When an atom or molecule undergo transition from higher energy level, E2 to lower
energy level E1 with an emission of photon of energy ℎ𝜈,the spectrum obtained is
called emission spectrum.
Based on the interacting species, the spectra can be divides as:

• Atomic Spectra:
APPLICATIONS
The spectrum arises from the transition of electrons between the atomic energy levels.
• Molecular Spectra:
The spectrum arises from the transition of electrons between different molecular energy
levels.
4. Explain the different molecular energy levels in a molecule?
A molecule possesses the following four types of energy.
• Electronic energy (Eel)
It is associated with the electrons present in a molecule, which can occupy various
molecular energy levels. It is due to the transition of electrons between the ground state to
excited electronic energy levels. The energy gaps between the electronic energy levels
falls in UV-visible region.
• Vibrational energy (Evib)
The molecules possess vibrational energy when atoms in the molecule vibrate by keeping
the center of mass constant. Vibrational transitions give absorption or emission spectrum
near the IR region.
• Rotational energy (Erot)
A molecule possesses rotational energy when it rotates about an axis perpendicular to the
inter nuclear axis passing through the center of mass. The energy gap between the
rotation energy levels falls in the microwave region.
• Translational energy (Etrans)
During the motion the center of mass of the molecule changes. Energy associated with
this motion is called Translational energy. It is negligibly small and usually not
quantized.
5. Most absorption bands in the electronic spectra are broad. Give reason.
Electronic transitions of a molecule are accompanied by vibrational and rotational
transitions. Also, the vibrational energy levels are accompanied by Rotational energy
levels. Thus the electronic transitions are appearing as broad band.
APPLICATIONS
6. State and explain Beer-Lambert’s Law?
According to this law, when a beam of monochromatic light is passed through a solution, the
decrease in intensity of radiation(-dI) with thickness of the absorbing material (x) is directly
proportional to the intensity of incident radiation(I) as well as to the concentration of the
solution(c).
−𝑑𝐼
∝ 𝐼𝑐
𝑑𝑥
−𝑑𝐼
= 𝑘𝐼𝑐
𝑑𝑥
−𝑑𝐼
= 𝑘𝑐𝑑𝑥
𝐼
Where k = proportionality constant
Let I0 = intensity of the incident radiation
I= intensity of the transmitted radiation. Then,
𝐼 𝑥
𝑑𝐼
−∫ = 𝑘𝑐 ∫ 𝑑𝑥
𝐼0 𝐼 0
𝐼 𝑥
∫ ln 𝐼 = 𝑘𝑐 ∫ 𝑑𝑥
𝐼0 0
Applying limit, we get,

𝐼0
𝑙𝑛 = 𝑘𝑐𝑥
𝐼
𝐼0
2.303 𝑙𝑜𝑔 = 𝑘𝑐𝑥
𝐼
𝐼0 𝑘
𝑙𝑜𝑔 = 𝑐𝑥
𝐼 2.303
APPLICATIONS
𝑘
But, 2.303 = 𝜀, Molar extinction coefficient or molar absorptivity
Thus,
𝐼0
𝑙𝑜𝑔 = 𝜀𝑐𝑥
𝐼
𝐼0
But, 𝐴 = 𝑙𝑜𝑔 thus, A= 𝜀𝑐𝑥
𝐼
This is the simplified form of Beer-Lambert’s law.
7. Explain the term molar absorptivity.

𝐴
From Beer- Lambert’s Law, 𝜀 = 𝑐𝑥
Where A= absorbance (dimensionless)
c = concentration of sample in moles/liters or moles/dm3
x = length of the light path or the thickness of the sample in dm
thus, the unit of 𝜀 = 𝑚𝑜𝑙 −1 𝑑𝑚2
def: It is the measure of amount of light absorbed per unit concentration and path
length.
UV SPECTROSCOPY
8. What are the different types of electronic transitions in UV spectroscopy?
→* n→* →* n→*

Electronic transition Electronic transition Electronic transition Electronic transition
occurs from  occurs from n occurs from  occurs from n
bonding orbital to bonding orbital to bonding orbital to bonding orbital to
the * anti bonding the * anti bonding the * anti bonding the * anti bonding
orbital. orbital. orbital. orbital.
APPLICATIONS
Transition energy is Transition requires Transition requires Transition requires
high. lesser energy. lesser energy. very lesser energy.
Saturated Compounds Organic unsaturated Organic unsaturated
hydrocarbons give containing O, S, N hydrocarbons hydrocarbons with
the transition. and halogens O, S, Cl etc.
E.g., CH4, C2H6 etc. E.g., CH3-OH, CH3- E.g., CH2=CH2, Eg, CH3-CHO, CH3-
Cl etc. benzene CO- CH3
9. Why methane and ethane does not show any peak by UV- visible
spectrophotometer?
The  bonded electrons are held firmly in the molecule. Hence this transition requires high
amount of energy and occur in the far UV region where the wavelength is approximately equal to
150nm. The saturated hydrocarbons can give only →* transition of C-C bond and C-H 
bond. Since this type of transition occurs below 150nm, normal UV-Visible transition (ranges
from 200-700nm) cannot be detect the saturated hydrocarbons.
APPLICATIONS
APPLICATIONS
APPLICATIONS
All are IR active compounds.

APPLICATIONS
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APPLICATIONS
APPLICATIONS
APPLICATIONS
Why TMS is chosen as reference in NMR spectroscopy?

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MODULE 1: SPECTROSCOPY AND ITS

2. What are the advantages of spectroscopy?

Based on the nature of interaction, the spectra can be divided as:

Based on the interacting species, the spectra can be divides as:

Applying limit, we get,

This is the simplified form of Beer-Lambert’s law.

7. Explain the term molar absorptivity.

→* n→* →* n→*

All are IR active compounds.

Why TMS is chosen as reference in NMR spectroscopy?

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