Jimma Uiniversity
College of Natural Sciences
Department of Chemistry
Instrumental Analysis II
Fanose Biru ([Link].)
1
1. Introduction to Spectroscopy
1.1. Electromagnetic Radiation and its interaction with matter
Spectroscopy - the science that deals with “interactions of
matter with electromagnetic radiation or other forms energy”
Matter – atoms, molecules & ions.
It deals with spectra to determine the chemical
composition/elucidate molecular structure and physical
properties of substances
Spectrophotometry: a more restrictive term,
any procedure that uses light to measure chemical
concentrations.
Spectroscopic analytical methods are based on measuring
the amount of radiation produced or absorbed by molecular
or atomic species of interest
Spectrometer- is an instrument design to measure the
spectrum of atoms or molecules
Cont…
The most interesting and common types of interactions are
absorption and emission of radiation by molecular or atomic
species of interest
This involves transitions between energy levels of molecules
or atoms
Other types of interactions are transmission, reflection,
refraction, scattering, interference, diffraction, and dispersion
w/c related to the bulk properties of materials rather than to
energy levels of specific molecules or atoms
Cont…
Electromagnetic radiation (EMR) – is a form of energy that is
produced by the movement of electrically charged particles
traveling through a matter or vacuum or by oscillating
magnetic and electric disturbance
It is a radiation that consists of discrete package of energy (
called photon)
photon exhibits properties of both waves and particles
This property is referred to as the wave–particle duality
These dual views of radiation as particles and waves are not
mutually exclusive but are complementary
The term light sometimes refers to EMR, particularly radiation
of a wavelength that is visible to the human eye (about 400–
700 nm)
The study of light, known as optics
Cont…
Electromagnetic spectrum
The frequency and wavelength of electromagnetic radiations
vary over a wide range.
For convenience the EMR is divided into different regions
known as the electromagenetic spectrum.
As a wave’s wavelength increases, the frequency decreases, and
as wave’s wavelength decreases, the frequency increases.
Electromagnetic radiation is grouped into categories based on its
wavelength or frequency into the electromagnetic spectrum.
Cont…
Wave nature
EMR can be described as oscillating electric and magnetic fields
that propagate through space.
photon consists of oscillating electric field and magnetic
field w/c are perpendicular to each other and also to the
direction of propagation of radiation
The wave nature EMR characterized by the following properties
Wavelength (λ) - is the distance of one full cycle of the oscillation.
Longer wavelength waves carry low energy. or
the distance b/n two consecutive peaks in the wave.
Frequency (ν) – is the number of complete oscillations that the
wave makes each second.
The number of peaks that pass a given point per second.
Its unit s-1 = hertz (Hz).
Cont…
This wavelength frequently relationship is characterized by:
C = λν
where
c is the speed of light,
λ is wavelength, and
ν is frequency.
Shorter wavelength means greater frequency, and greater
frequency means higher energy.
Wavelengths are important in that they tell one what type of
wave one is dealing with.
Cont…
Frequency is directly proportional to energy and can be express as:
E = hν where
• E is energy,
• h is Planck's constant, (h= 6.62607 x 10-34 J), and
• ν is frequency.
Wave number (ύ) –is the number of cycles contained in each unit of
length usually centimeter of wave .
it is reciprocal of the wavelength ῡ = 1/λ
Period (p) - is the amount of time a wave takes to travel one wavelength; it is
measured in seconds (s).
Amplitude - the height of the wave
Velocity (c) – the rate at which the wave moves
In vacuum (v = c = 3.0 x 108m/s).
In other medium (v = c/n, where n is refractive index of the medium).
For visible wavelengths in most substances, n > 1, so visible light
travels more slowly through matter than through vacuum.
When light moves between media with different refractive indexes, the
frequency remains constant but the wavelength changes.
Example: A characteristic of yellow light emission of sodium from
street lamp occurs at a wave length of 589 nm. Calculate its
frequency, wavenumber and energy.
Solution
(i) ν = c/λ = (3.0 x 108 m/s)/ (589 x 10-9m) = 5.09 x 1014 s-1
(ii) ῡ = 1/λ= 1/ 589 x 10-9 =1.7-12 m-1
(ii) E = hν = 6.626 x 10-34 J s x 5.09 x 1014 s-1 = 3.38 x 10-19 J
Exercise:
(1) By how many kilojoules per mole is the energy of O2 increased
when it
absorbs ultraviolet radiation with a wavelength of 147 nm? How much
is the energy of CO2 increased when it absorbs infrared radiation with a
wavenumber of 2 300 cm-1? (6.022 x1023 = molecules/mol).
(2) What is the wavelength, wavenumber, and name of radiation with an
energy of 100 kJ/mol?
(3)The red light frequency is approximately 4.3×1014 Hz. Calculate its
wavelength and wave number?
Particle nature
The need for a particle model to describe the behavior of
electromagnetic radiation can be seen by consideration of the
photoelectric effect
Photoelectric effect - is a phenomenon in which electrons are ejected
from the matter exposed to light of at least a certain minimum
frequency, called the threshold frequency as a consequence of
absorption of radiation
Electrons emitted is referred to as "photoelectrons“
This not be explained by the wave theory of light”
Photon is particle of light carrying
an amount of energy equal to hν
The energy of a single photon to its
wavelength, frequency, and
wavenumber by
𝒉𝒄
𝑬 = 𝒉𝒗 = = 𝐡𝐜ῡ
𝝀
h is Planck’s constant (6.63 x 10-34 J. s)
To remove electrons from the atom of matter require light or EMR of a
sufficiently high frequency (w/c corresponds to high energy) Since
electrons are held in atom of matter by attractive forces
If the frequency of photons is exactly equal to the energy that binds the
electrons in the atom of matter, the light / EMR will have enough
energy to knock the electrons loose
But If frequency of light/ EMR is higher, the electrons will be
knocked loose and acquire some kinetic energy
Where; KE -is the kinetic energy of the ejected electron and BE - is the
binding energy of the electron or a minimum energy required to eject an
electron or electrons
vo - is threshold frequency
So, kinetic energy of the ejected electrons increases linearly with the
frequency of the incident radiation, but independent of the radiation
intensity.
So, the experimental characteristics of the photoelectric effect are:
No electrons are ejected, regardless of the intensity of the radiation,
unless its frequency exceeds a threshold frequency value
Cont…
Increasing the radiation intensity will increasing the number
of incident photons w/c causes to increase the number of
ejected electrons or photoelectrons and the rate at which
photons strike the surface of the metal
Electrons are ejected immediately if the frequency is above
the threshold even at low light intensities
Albert Einstein proposed that light had both wave and
particle properties
He’s assumption is an electron ejected when struck by a
single photon w/c implies that it behaves like a particle
He further showed that photons do have relativistic mass
(m) moving with speed of light (c) were given by equation:
Louis de Broglie postulated that a particle with mass m and a velocity
c = u has an associated with wavelength
ᴧ → Wave nature, m → Particle nature
mc - is the momentum (p) of a photon
1.3. Absorption and Emission of Radiation
Principle of spectroscopy
is based on the measurement of spectrum of a sample containing
atoms or molecules
Electromagnetic spectrum is the range of wavelength over which EMR
extends
Or the division of electromagnetic radiation on the basis of a photon’s
energy.
Spectrum is defined as the characteristic wavelengths of
electromagnetic radiation (or a portion thereof) that is emitted or
absorbed by an object or substance, atom, or molecule.
Absorption
In absorption spectroscopy the energy carried by a photon is absorbed
by the analyte, promoting the analyte from a lower-energy state to a
higher-energy, or excited, state or
Absorption is Interaction of EMR with matter results in transfer of
energy from the beam of the radiation to the matter.
this transfers the matter from a lower to a higher energy state (excitation).
It is a process of radiation’s intensity attenuation
The intensity of photons passing through a sample containing the
analyte is attenuated because of absorption.
It is process of transfers energy and results in a decrease in the
intensity of the incident electromagnetic radiation.
The measurement of this attenuation, which we call absorbance, serves
as our signal
• NB: the transfer is possible if the energy of the photons is exactly the same
or greater than energy difference between the two energy levels of the atom
or molecule.
Cont…
When a molecule absorbs a photon, the energy of the molecule
increases.
Ex., IBr
Emission of radiation – is a process in w/c the radiation is emitted when
the excited species return to their ground state
Light enters a Light leaves a
sample sample
Emission spectrum – is a spectral lines or bands that are observed when
species in excited states relax by giving off their excess energy as
electromagnetic radiation
Notice:
● Absorption of light increases the energy of a molecule.
● Emission of light decreases its energy.
When a molecule absorbs a photon, the energy of the molecule increases.
We say that the molecule is promoted to an excited state
If a molecule emits a photon, the energy of the molecule is lowered.
The lowest energy state of a molecule is called the ground state.
Example: By how many kilojoules per mole is the energy of
O2 increased when it absorbs ultraviolet radiation with a
wavelength of 147 nm?
At room temperature, most substances are in their lowest energy or
ground state
Excitation can be brought about by a variety of means, including
bombardment with electrons or other elementary particles,
exposure to a high-potential alternating current spark,
heat treatment in an arc or a flame,
absorption of electromagnetic radiation, or
chemical reaction.
Emission following the absorption of a photon is also called
photoluminescence, and Emission following a chemical reaction is
called chemiluminescence
1.4. The electromagnetic spectrum
All rays of EMR have the same velocity but different energy (E),
wavelength (λ) and frequency (ν)
Electromagnetic spectrum - is arrangement of components of the
EMR according to increasing or decreasing order of energy (either the
frequency or wavelength of their wave)
• Therefore, Electromagnetic radiation is divided into different regions
based on the type of atomic or molecular transition that gives rise to
the absorption or emission of photons
• The boundaries describing the electromagnetic spectrum are not rigid,
and an overlap between spectral regions is possible
Spectroscopists use the absorption and emission interactions of
radiation with matter which are called absorption and emission
spectroscopy, respectively to obtain information about a sample
In these classes of techniques, energy is transferred between a
photon of electromagnetic radiation and the analyte