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Spectroscopy
It is a branch of science that deals with interaction of matter with light or electromagnetic
radiation.
OR
Spectroscopy is a branch of science in which electromagnetic radiation of particular wavelength or range
of wavelength is used for qualitative and quantitative analysis of matter.
Spectrum is a graph or plot of intensity of absorbed/ emitted radiation sample verses frequency or
wavelength. Spectrophotometer is an instrument to measure the spectrum of a sample. Spectroscopic
techniques possess numerous merits over classical techniques as:
• It takes less time.
• Require very small amount of the compound being studied
• Very fast and economical in long run.
• Non-destructive i.e. the compound being studied remain unchanged and can be usedfor other
tests.
• Highly reliable in establishing the identity of two compounds.
• Information can be recorded in the form of a permanent chart in an automatic orsemiautomatic
manner.
Electromagnetic radiations
Electromagnetic radiations are wave produced by motion of electrically charged particles (Photon).
It consists of two components –Electric and Magnetic
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Electromagnetic field produce electromagnetic radiation also referred to as EM radiation.
Electromagnetic radiation is a form of energy that is present all around us and takes various forms
like microwaves, television waves, radio waves, gamma rays, X-rays, etc.
Electromagnetic radiation can be defined as a form of energy that is produced by the
movement of electrically charged particles travelling through a matter or vacuum.
The magnetic and the electric fields come at 90° to each other, and the combined waves move
perpendicular to both electric and magnetic oscillating fields occurring the disturbance.
Properties of Electromagnetic Radiation
1. When electromagnetic radiation occurs, the electron radiations are released as photons.
2. These are bundles of light energy or quantized harmonic waves which travel at the speed of
light.
3. These magnetic and electric waves travel perpendicular to each other and have some
characteristics like wavelength, amplitude, and frequency.
4. They can travel through empty space. Waves other than electromagnetic waves have to travel
through some substance. For example, sound waves will need either a solid, liquid or gas to pass
through.
5. The speed of light which is 2.99792458 x 108 m/s is always constant.
6. Examples of EM radiation include radio waves and microwaves, as well as infrared,
ultraviolet, gamma, and x-rays. Some sources of EM radiation include sources in the cosmos (e.g.,
the sun and stars), radioactive elements, and manufactured devices.
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Waves and their Characteristics
Electromagnetic waves and their characteristics is explained briefly in the points mentioned
below.
Wavelength
Wavelength (λ) is the distance between successive crests of a wave, It can be simply defined as the
distance of one full cycle of the oscillation. If ‘λ’ is the wavelength, ‘c’ is the speed of light and ‘ν‘ is
frequency. Then we can derive the relation given below.
c=λν
The shorter the wavelength, greater the frequency and greater the frequency, the higher the energy.
Units to measure: nm, cm, m
Amplitude
It is the distance from the middle of the wave to the maximum vertical displacement of the wave.
Larger the amplitude, higher the energy and lower the amplitude, lower the energy.
Amplitude tells us about the brightness or intensity of a wave compared to other waves.
Frequency
The number of cycles per second is defined as Frequency. It is measured in Hertz (Hz) or sec-1.
If ‘E’ is the energy, ‘h’ is Planck’s constant, which is equal to 6.62607 x 10-34and ‘ν‘ is the
frequency we can derive the relation given below.
E = hν
Thus, we can see that frequency is directly proportional to energy.
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Wave number
The term wave number refers to the number of complete wave cycles of an electromagnetic
field (EM field) that exist in one meter (1 m) of linear space. Wave number is expressed in
reciprocal meters (m-1).
Period
Period is commonly characterized by the symbol ‘T’. It is the total time which a wave takes to travel
1 wavelength.
Velocity
In relation with electromagnetic radiation, the velocity is normally expressed as:
Velocity = λν
[where, ν = frequency]
The wave velocity in vacuum for electromagnetic wave is = 186,282miles/second or
2.99×108 m/s.
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Electromagnetic Spectrum
Accelerating charges produce electromagnetic waves. There are many levels in the structure of
matter where moving (accelerating) charges exist.
Many different types of EM waves are categorized according to their origins and their
frequency/wavelength values.
The electromagnetic spectrum is arrangement of all electromagnetic waves according to
frequency and wavelength.
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Important Uses of Electromagnetic radiation:
Types of Electromagnetic Spectrum based on its origin:
Emission Spectrum
• Whenever electromagnetic radiation interacts with atoms and molecules of matter, the
electrons in these atoms may absorb energy and jump to a higher energy state, losing their
stability.
• In order to regain their stability, they need to move from the higher energy state to the
previous lower energy state.
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• To accomplish this job, these atoms and molecules emit radiation in various regions of the
electromagnetic spectrum.
• This spectrum of radiation emitted by electrons in the excited atoms or molecules is
known as an emission spectrum.
Absorption Spectrum
• An absorption spectrum is like a photographic negative of an emission spectrum.
• For observing the absorption spectrum, electromagnetic radiations are bombarded on a
sample that absorbs radiation of certain wavelengths.
• The wavelength of radiation absorbed by the matter contributes to the missing wavelength,
which leaves dark spaces in the bright continuous spectrum.
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Emission Spectra VS Absorption Spectra
Emission Spectra Absorption Spectra
Produced when atoms release energy Produced when atoms absorb
energy
Comprise coloured lines in the Comprise dark lines or gaps in the
spectrum spectrum
Emission spectra can emit all the while the absorption spectrum can
colours in an electromagnetic have a few colours missing due to
spectrum, the redirection of absorbed photons.
Electrons move from higher energy Electrons are excited to higher
level to lower energy level while energy level during absorption of
emitting light. light.
Emission of light happens in the Require a source of energy to
absence of source. absorb light.
The type of photons emitted is helpful The wavelengths of light
in figuring out the kind of elements absorbed is helpful in figuring out
present in the the substance as each the number of substances in the
element radiates a different amount of sample.
energy and has a unique emission level
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Interaction of matter with radiations
Interaction of matter with radiations
Absorption of light
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Emission of light
NOTE: Absorption spectroscopy and not Emission spectroscopy is used to study the spectra
of organic compound
Because emission of radiation from an organic compound requires very high temperature where
organic compounds generally decompose and it affect the properties of organic compounds.
Continuous spectrum
It consists of unbroken luminous bands of all wavelengths containing all the colours from violet to
red. Carbon arc, electric filament lamps etc, give continuous spectra.
This kind of spectrum is called a continuous spectrum as violet merges into blue, blue into green and
so on.
Line spectra (Atomic spectra)
Line spectrum (also called atomic spectrum) is produced when atom of a particular element is
irradiated with energy*, causing excitation of outer shell electron(s) to higher state. When these
electron(s) return to their ground state, they emit their excitation energies corresponding to a
particular frequency (and hence a particular wavelength, for the medium). This in spectroscopy
shows as line. (Characteristic of an element)
Line spectra are sharp lines of definite wave lengths. It is the characteristic of the emitting substance so is used
to identify the gas.
Band Spectrum (Molecular Spectra)
It consists of a number of bright bands with a sharp edge at one end but fading out at the other end. Band
spectra are obtained from molecules. It is the characteristic of the molecule.
If a Molecule (may be of same or different element) is irradiated, apart from the excitation- there
will be additionally rotational or vibrational movements taking [Link] appears as several line
spectrum ,cluster of these fine lines form a band and the spectra is known as Band Spectrum.
INTERACTION OF EMR WITH MATTER
EMR interacts with matter only when the matter has some electric and magneticeffect and are
influenced by the electric and magnetic components of the EM radiation.
The net change is observed in the electric/magnetic dipole moment in the molecule or in nuclear
spin when matter interact with the magnetic/electrical component of the EMR by either absorption
or emission of the EMR.
Total energy of molecules = Translational + rotational + vibrational + electronic
Absorption or emission of EMR causes a change in any of these types of energiesin molecular
spectroscopy, we measure the change in these energy states.
Translational energy – It is due to the overall movement of the molecule. This is very small
value , energy levels are not quantized . Hence it is not considered for spectroscopy.
Rotational energy – It is due to spinning of molecules about the axis passing through the
centre of gravity or rotation of molecule. Transition is observed between rotational levels. This
transition is observed in Rotational spectroscopy (Microwave spectroscopy)
Vibrational energy – It is due to vibrations in molecules – c a u s i n g t r a n s i t i o n
b e t w e e n vibrational levels. This is considered as IR Spectroscopy (Vibrational
spectroscopy)
Electronic energy – Causes transition within electronic levels–This is considered as
UV/visible spectroscopy (Electronic spectroscopy)
If E is the total energy of a molecule, it can be expressed as the sum of translational,
rotational, vibrational and electronic contributions.
E = Etrans +Erot + Evib + Eelec
1. Rotational Changes:Microwave spectroscopy:
2.
Vibrational Changes:IR spectroscopy:
3.
Changes at electronic level along with vibrational and rotational changes:UV-
Visible spectroscopy:
Application of Molecular spectroscopy (very important)
Different types of spectroscopic transition and required criteria:
Q. Mention the criteria the molecule should possess to exhibit rotational spectra.
In which region of the electromagnetic spectrum does it occur? The transition
among which energy levels lead to Rotational spectra/Raman spectroscopy/Electronicspectroscopy
NUMERICALS:
Numerical Problems
1. Calculate the energy of a photon of radiation with a frequency of 8.5 x 1014 Hz.
2. Calculate the energy of a photon of radiation with a wavelength of 6.4 x 10-7 m.
3. An FM radio station broadcasts at a frequency of 107.9 Hz. What is the wavelength of the radio signal?
4. Calculate wavelength and frequency and wavenumber of a light. whose period is 2×1010 second.
5. The color orange within the visible light spectrum has a wavelength of about 620nm. What is the
frequency and energy of orange light?
Flame photometer
The principle of flame photometer is based on the measurement of the emitted light intensity when a metal is
introduced into the flame.
The wavelength of the colour gives information about the element and the colour intensity of the flame gives
information about the amount of the element present in the sample.
Flame photometry is one of the branches of atomic absorption spectroscopy. It is also known as flame emission
spectroscopy. Currently, it has become a necessary tool in the field of analytical chemistry.
Flame photometer can be used to determine the concentration of certain metal ions like sodium, potassium,
lithium, calcium and cesium etc.
Principle of Flame photometer
The compounds of the alkali and alkaline earth metals (Group II) dissociate into atoms when introduced into
the flame. Some of these atoms further get excited to even higher levels. But these atoms are not stable at
higher levels.
Hence, these atoms emit radiations when returning to the ground state. These radiations generally lie in the
visible region of the spectrum. Each of the alkali and alkaline earth metals has a specific wavelength.
The intensity of the emission is directly proportional to the number of atoms returning to the ground state. And
the light emitted is in turn proportional to the concentration of the sample.
Parts of flame photometer
A simple flame photometer consists of the following basic components:
Source of flame: A Burner in the flame photometer is the source of flame. It can be maintained in at a constant
temperature. The temperature of the flame is one of the critical factors in flame photometry.
Requirement from Flame
• It should have proper temperature
• Temperature should remain constant throughout the operation
• There should not be any fluctuation during burning
Functions of Flame
• To convert the analyte of the liquid sample into vapour state.
• To decompose the analyte into atoms and simple molecules.
• To excite the formed atoms/free atoms/simple molecules to emit radiant energy.
Nebulizer: Nebulizer is used to send homogeneous solution into the flame at a balanced rate. It breaks up the
liquid into small droplets.
Optical system: The optical system consists of convex mirror and convex lens. The convex mirror transmits
the light emitted from the atoms. Convex mirror also helps to focus the emissions to the lens. The lens helps
to focus the light on a point or slit.
Simple colour filters: The reflections from the mirror pass through the slit and reach the filters. Filters will
isolate the wavelength to be measured from that of irrelevant emissions.
Photo-detector: The intensity of radiation emitted by the flame is measured by photo detector. Here the
emitted radiation is converted to an electrical signal with the help of photo detector. These electrical signals
are directly proportional to the intensity of light.
Procedure:
• The solvent is first aspirated to obtain fine solid particles.
• These molecules in the solid particles are moved towards the flame to produce gaseous atoms and ions.
• These ions absorb the energy from the flame get excited to high energy levels from the ground state.
• But as these ions are unstable, they return to ground state. While returning they emit characteristic radiation.
• The intensity of emitted light is proportional to the concentration of the element. The oxidants in flame
photometer are mainly air, oxygen or nitrous oxide. The temperature of the flame depends on the ratio of fuel
and oxidant.
The processes occurring during flame photometer analysis are summarized below:
Desolvation: involves drying a sample in a solution. The metal particles in the solvent are dehydrated by the
flame and thus solvent is evaporated.
Vaporization: The metal particles in the sample are also dehydrated. This also led to the evaporation of the
solvent.
Atomization: Atomization is the separation of all atoms in a chemical substance. The metal ions in the sample
are reduced to metal atoms by the flame.
Excitation: The electrostatic force of attraction between the electrons and nucleus of the atom helps them to
absorb a particular amount of energy. The atoms then jump to the higher energy state when excited.
Emission: Since the higher energy state is unstable the atoms jump back to the ground state or low energy state
to gain stability. This jumping of atoms emits radiation with characteristic wavelength. The radiation is
measured by the photo detector.
Applications of flame photometer
1. Flame photometer can be applied both for quantitative and qualitative analysis of elements. The
radiations emitted by the flame photometer are characteristic to particular metal. Hence, with the help
of Flame photometer we can detect the presence of any specific element in the given sample.
2. The presence of some group II elements is critical for soil health. We can determine the presence of
various alkali and alkaline earth metals in soil sample by conducting flame test and then the soil can be
supplied with specific fertilizer.
3. The concentrations of Na+ and K+ ions are very important in the human body for conducting various
metabolic functions. Their concentrations can be determined by diluting and aspirating blood serum
sample into the flame.
4. Soft drinks, fruit juices and alcoholic beverages can also be analyzed by using flame photometry to
determine the concentrations of various metals and elements.
5. Used in determination of calcium and magnesium in cement.
6. Used in determination of lead in petrol.
Advantages of flame photometer
1. The method of analysis is very simple and economical.
2. It is quick, convenient, selective and sensitive analysis.
3. It is both and qualitative and quantitative in nature.
4. Even very low concentrations (parts per million/p pm to parts per billion/ppb range) of metals in the
sample can be determined.
5. This method can be used to estimate elements, which are rarely analyzed.
Disadvantages of flame photometer
In spite of many advantages, this analysis technique has quite a few disadvantages:
1. The accurate concentration of the metal ion in the solution cannot be measured.
2. It cannot directly detect and determine the presence of inert gases.
3. Though this technique measures the total metal content present in the sample, it does not provide the
information about the molecular structure of the metal present in the sample.
4. Only liquid samples may be used. Also, sample preparation becomes lengthy in some cases.
5. Flame photometry cannot be used for the direct determination of each metal atom. A number of metal
atoms cannot be analyzed by this method. The elements such as carbon, hydrogen and halides cannot
be detected due to their non-radiating