Fundamentals of
Spectroscopy
Ms. Pooja R. Popat
HVHP Institute of post graduate studies
and Research,
Kadi Sarva Vishwavidyalaya
Spectroscopy
Properties of light
Interaction of light with matter and origin of spectra
Difference between molecular and atomic spectra
EMR- Electromagnetic radiation
• Form of energy emitted or absorbed by charged particles
which exhibits wave like nature.
• Travels through space with same velocity of light
• (a) Corpuscular theory – Particle nature
(b)Wave theory – Wave nature
Characteristics of EMR
• Oscillation of electric field and Magnetic field – Perpendicular
• Characterized by Wave length, Wave number and frequencies.
• No requirements of Medium, dislike sound
What is called photons?
The absorption / emission or radiant energy can not be explained
by making use of wave model of radiation.
For these process, it is necessary to view EMR as discrete particles
of energy is called photons.
The energy of photons is directly proportional to the frequency of
radiation.
Ep α Frequency of radiation
• Wave length (λ) – Distance between two nearest crest or
trough - (Units - cm, m, nm)
• Frequency – The no. of Waves passing from one point per
second – [units - cps (Hz)]
• Amplitude – Height of Peak or Crest
• Wave number(ῡ) – Total number of Waves present in one
cm. [Unit – Cm-1]
Or
Reciprocal of wave length
• Energy – The energy of photons is related to the frequency
of the wave. [Unit – Joule /mole]
Electromagnetic spectrum
• Radiowaves – Nuclear and Electron spin (Nuclear energy)
• Microwaves – Rotational energy (Change in dipole moment
– Polar Molecules)
• IR – Vibrational energy (Change in dipole moment)
• Uv-Visible – Electronic energy - Valence electrons
• X- rays – Inner electrons
• Gamma rays – Nuclear configuration
Spectroscopy is one of the most powerful tools available for the
study of atomic and molecular structure and is used in the analysis
of a wide range of a sample.
The study of Spectroscopy can be carried out under the following
two heads:
(1) Atomic spectroscopy
In this spectroscopy, atoms of the sample are interact with EMR.
(2) Molecular spectroscopy
In this spectroscopy, molecules of the sample are interact with
EMR.
Molecular Spectroscopy based on ultraviolet, visible and infrared
radiation to widely used for the identification and determination of
many inorganic, organic species.
Properties of light:
Light is part of the electromagnetic spectrum, which ranges
from radio waves to gamma rays.
(1) Diffraction of radiation
(2) Dispersion of radiation
(3) Refraction of radiation
(4) Reflection of radiation
(5) Scattering of radiation
(6) Polarization of light
(1) Diffraction of radiation:
EMR normally travels in straight paths, but a beam of radiation
is allowed to pass through a sharp edge or through a narrow
opening, a part of it appears in areas that should be in the
shadow of the object in its path of travel
Blending of radiation is called diffraction.
Diffraction occurs when a wave encounters an obstacle.
(2) Dispersion of radiation:
The index of refraction of an optical medium is an important bulk
property and may be defined as the ratio of the velocity of radiation of
a particular frequency in vacuum to that in the medium.
The variation of refractive index of a substance with frequency or
wavelength is called dispersion.
It is related to the degree to which radiation is absorbed.
There are two types of dispersions:
(a) Normal Dispersion: Normal dispersion occurs in that region in
which the refractive index increases gradually with increasing
frequency or decreasing wavelength.
(b) Anomalous Dispersion: anomalous dispersion takes place in that
region in which a short change in refractive index is observed.
(3) Refraction of radiation:
When a beam of radiation is
allowed to pass from one
medium to another having
different physical density than
the first, an immediate change
in the direction of the beam is
observed.
This is due to the differences in
the velocity of radiation in two
media.
This phenomenon is called
refraction.
The change in direction of
wave due to change in its
medium is known as
refraction.
(4) Reflection of radiation:
It can be defined as the bouncing back of a ray of light into
the same medium when it strikes a surface.
(5) Scattering of radiation:
When a turbid solution i.e. a suspension of solid
particles in a liquid, is brought into the light path of a
photometer, less radiant power reaches the photo
detector than if a non absorbing clear liquid were in
the light path.
This reduction results from the scattering of light due to
reflection on and refraction by the suspended particles.
The scattering of light by molecules can be explained by
making use of electromagnetic theory.
Scattering by molecules or aggregates of molecules with
dimensions smaller than the wavelength of the radiation is called
Rayleigh scattering.
Measurement of scattered radiation can be used to determine the
size and shape of polymer molecules and colloidal particles.
The phenomenon is also applied in nephlometry and
turbidimetry.
Raman effect is phenomenon due to which the scattering
light has slightly different frequency from that of the
incident light and there is thus a change in the atomic
oscillations within the molecules.
(6) Polarization of light
Light waves are said to exhibit
polarization when they show lack of
symmetry about the direction of
propagation of light.
. If a beam of polarized light
proceeding in a straight line has all
its vibrations in one plane, i.e., at
right angles to propagation of light, it
is said to be Linear and Plane
Polarized. Similarly, it is said to be
circularly polarized when the
vibrations are along a circle and the
direction of the execution of the
circle does not change with time.
1) Linear and Plane Polarized.
2) Circularly polarized
It should be noted that ordinary light does not
exhibit polarization, because when it is
examined with a single rotating tourmaline
crystal, no variations in intensity of emergent
light is observed.
Hence ordinary light may be regarded as un
polarised light. Linear
When a plane polarised light is passes through
solution of certain substance, such as can sugar,
the plane of polarization is rotated and such
substances are said to be optically active.
These substances which cause rotation to the
right have been named dextro rotary (d) and
those which cause rotation to the left are levo
rotatory (l).
Circular
Interaction of light with matter and origin of spectra:
When electromagnetic radiation passes from a vacuum to
the surface of a portion of matter, the electrical vector of the
radiation interacts with the atoms and molecules of the
medium.
As a consequence the radiation may either be
Absorbed
Transmitted
Reflected
Scattered.
Absorption of Light:
Absorption is the process in which certain frequencies may
be selectively removed when a beam of radiation is allowed
to pass or molecule absorbs energy, the atom or molecule
will move to a higher energy state or excited state.
Why red solution is red?
A solution such as Fe(SCN)+2 is not red because it absorbs green from
the incoming white radiation and transmits the red component.
Thus in a colorimetric determination of iron based on its thiocyanate
complex, the maximum change in absorbance with concentration occurs
with green radiation.
Wavelength (nm) Color of light absorbed Complementary color
transmitted
400-435 Violet Yellow-green
435-480 Blue Yellow
480-490 Blue-green Orange
490-500 Green-blue Red
500-560 Green Purple
560-580 Yellow-green Violet
580-595 Yellow Blue
595-650 Orange Blue-green
650-750 Red Green-blue
In this manner, the electromagnetic energy is transferred to the atoms
or molecules comprising the sample.
E0 represents the ground energy state and E*, the excited electronic
state.
An electron is capable of undergoing transition from E0 to E* state,
if energy in the form of light or heat is absorbed.
This adsorption radiation causes the molecule or atom to be in an
excited state.
Excited atoms or molecules are relatively short lived, and tend to
return to their ground state after approximately 10-8 sec.
Hence from the excited level, the electron may return to its normal
position either directly or in steps with the emission of certain
amount of energy.
When this emission of light is instantaneous, the phenomenon is
known as fluorescence, but when after some time lag, it is
known as phosphorescence.
When the absorbed energy is stored by the atom or
molecule and used in producing some chemical reaction,
fluorescence and phosphorescence become absent and
the resulting chemical reaction is called photo-chemical
reaction.
Here, the movement of an electron from E0 to E*
(absorption) requires the addition of energy and the energy
for this transition is equal to the difference between two
energy levels.
In emission, the electron comes down from E* to E0 with
the emission of a photon and the energy of radiation
emitted will be equal to the difference between E0 and E*
levels.
Difference in the origin and appearance of molecular
and atomic spectra:
The atoms in the molecule can vibrate and rotate with
respect to one another.
These vibrations and rotations have discrete energy states.
A number of vibration and rotational energy levels are
packed on top of each electronic level.
From that we can say that electronic transition require the
most energy, while rotational transitions require the least
energy.
Transition from Vibrational and rotational energy levels
within ground state to the corresponding Vibrational and
rotational levels within the excited electronic state is also
possible.
The resulting spectra is called band spectra and appears
to be broad.
In the case of an atom, the species neither vibrate nor
rotate, as a molecule does.
Thus the atom does not have vibrational and rotational
energy levels.
Hence transition between energy levels of an atomic
species results in very sharp lines.
Whether the radiation absorbed or emitted by a species is
from molecule or atom, may be ascertained by the fact
that a molecule produces a band spectrum and the
atom a line spectrum.
Ms. Pooja R. Popat
HVHP Institute of post graduate studies
and Research,
Kadi Sarva Vishwavidyalaya