SPECTROSCOPY

EM waves carry energy and transfer their energy

upon interaction with matter.
Advantages of spectroscopic methods over
classical methods
• Requires less time
• Less amount of sample needed
• Results obtained are reliable ,reproducible and accurate
• Sample materials remain unchanged during analysis and
can be reused
Electromagnetic radiation :
Electromagnetic radiation consists of electrical and magnetic waves oscillating
perpendicular to each other.
They travel with velocity of light in vacuum.
The frequency and wavelength are related by v=c/⅄
EM radiation has the properties of both particles and waves.
The particles are called photons, and each possesses an amount of energy referred
to as a quantum.
Energy of a photon E=hv
light viewed as discrete particles of energy called
photons.
like other particles, light can be scattered, counted
(quantized) , etc

E = hѵ = hc/λ

h = Plank’s constant (6.63 x 10-34 J.S)

ѵ = frequency, λ= wavelength,
 Electromagnetic spectrum
• The electromagnetic spectrum is the distribution of electromagnetic radiation
according to energy or, equivalently, according to the wavelength or frequency.
• Based on the nature of interaction spectra can be divided into absorption
and emission spectra.
Absorption spectrum
If electromagnetic radiations of certain wavelength range are passed through the substance
under analysis, radiations of certain wavelengths are absorbed by the substance. The study
of this is called the absorption spectroscopy.
When an atom or a molecule undergoes transition from the lower energy level to the higher
one with the absorption of a photon energy hv (which is exactly equal to the energy
difference between the two levels), the spectrum obtained is called absorption spectrum.
Example: UV,IR,NMR, Microwave
Emission spectrum
If thermal energy is given to the substance under analysis, the energy is absorbed by the atom.
The electrons in the ground state get excited to higher energy metastable states. These excited
electrons are short lived. So they emit energy to return to the stable state. The study of this is
called the emission spectroscopy.
When an atom or molecule undergo a transition from higher energy level to lower energy level
with an emission of a photon of energy hv, the spectrum obtained is called emission spectrum.
Higher energy states have to be more populated than lower energy states.
Example: atomic emission spectrum, fluorescence spectrum, Hydrogen spectrum.
Atomic spectra & molecular spectra(based on
interacting species)
Atomic spectra
• interaction of atoms with electromagnetic radiation.
• Line spectra.
• Arise from transition of electrons between the atomic energy levels

• due to electronic transition in an element

Molecular spectra
• interaction of molecules with electromagnetic radiation
• complicated spectra
• Arise from transition of electrons between different molecular energy levels
• due to vibrational, rotational and electronic transition in a molecule
 Molecular energy levels
a) Electronic energy: It is associated with the electrons present in a
molecule, which can occupy various molecular energy levels. It can
be bonding or antibonding.
Energy gap between electronic energy levels falls in uv-visible
region.
b)Vibrational energy: Atoms in a molecule can vibrate by keeping the
position of centre of mass constant, the energy associated is called
vibrational energy.
Energy gap falls in IR region.
c)Rotational energy: If a molecule rotate in space about an axis passing
through its center of mass, it is said to possess rotational energy.
Rotational energy is possessed only by molecules of a gas or a liquid.
Energy gap falls in microwave region.

d) Translational energy: If the position of centre of mass changes with

the time the molecule is said to be possess translational energy. It is
usually not quantized.

Total energy of molecule is

Etot= Evib+Erot+Eel+Etran
Eel >> Evib>>Erot>>Etrans Etot= Evib+Erot+Eel
Translational energy is negligibly small
Electronic transitions are always accompanied by vibrational and rotational transitions.
Vibrational transitions are always accompanied by rotational transitions.
Molecules possess different quantum mechanical energy states such as
electronic, vibrational, rotational and nuclear.
The transition can occur between these states by the absorption or
emission of radiation.
These transitions are abided by quantum mechanical selection rules.
Spectroscopy involves the production, measurement and interpretation of
electromagnetic spectra arising from the emission or absorption of
electromagnetic radiations by atoms or molecules.
Detailed information regarding the structure and bonding , various inter
and intra molecular processes can be obtained from the analysis of atomic
and molecular spectra.
 Beer –Lambert’s law
• When a parallel beam of monochromatic electromagnetic radiation is
passed through an absorbing solution of given concentration (c) , the
rate of decrease of intensity (-dI) of radiation with the thickness of the
solution (dx) is proportional to the intensity of incident radiation (I) and
also to the concentration ( c) of the solution.

Mathematically ,
-dI/dx α Ic…………..(1)
Negative sign indicates ‘I’ decreases as ‘x’ increases

-dI/dx = KIc…………..(2)
Where k is proportionality constant
-dI/I = Kcdx (differential form of Beer Lambert’s law)
Let I0 be the intensity of incident radiation and I the intensity after passing through any finite thickness x of the medium, then

( logarithamic form of Beer lambert’s law)

Here ε = k/2.303 is called molar extinction coefficient or molar absorptivity . It is constant at any given
wavelength for given species.
Term log (I0/I) is known as absorbance and denoted as A. Absorbance is the logarithm of ratio of intensities
of incident light to the transmitted light .
Then A=εCx ( simplified form of Beer Lambert’s law)
The ratio between intensities of transmitted to incident light ( I / I0 ) is defined as Transmittance , T=I/I0

A = −log(T)
−log(T) = A = εCx
The exponential form of Beer Lambert’s law is I= I0 e-kcx

Units

C= moles/litre or moles/dm3
X=dm
ε=mol -1 dm2
According to Lambert-Beer’s law ,there exist a linear relationship between absorbance and
concentration.
A plot of A vs C yields a straight line passing through the origin indicating conformity to the law.
❖For a parallel beam of monochromatic radiation passing
through homogeneous solutions of equal path length,
the absorbance is proportional to the concentration.

❖For a parallel beam of monochromatic radiation passing

through homogeneous solutions of equal concentration, the
absorbance is proportional to the path length
Limitations of Beer –Lambert’s law
The linearity of the law is limited by chemical and instrumental facts. Cause of non-linearity
include:

• scattering of light due to particulates in the sample

• Fluorescence or phosphorescence of the sample
• Changes in the refractive index at high analyte concentrations
• non monochromatic radiation
• when the absorbing compound, dissociates, associates, or reacts with a solvent to produce
a product having a different absorption spectrum
• At high conc., the analyte molecules interact with each other, they can alter their ability to
absorb the radiation.