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RMG MAHESHWARI ENGLISH HIGH SCHOOL

NAME :- SMITA S. MANDAL

STANDARD :- 11- SCIENCE

SUBJECT :- CHEMISTRY

TOPIC :- ANALYTICAL CHEM. (SPECTROSCOPY)

ACADEMIC YEAR :- 2022-23

SUBMITTED TO :- CHINTAN PANCHAL

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ACKNOWLEDGEMENT
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INDEX
1. INTRODUCTION

2. ELECTROMAGNETIC RADIATION (EMR)

o Characteristics

3. SPECTROPHOMETER

o Characteristics
o Examples

4. INFRARED SPECTROSCOPY (IR)

o Effects Of IR On Molecules

5. VISIBLE & UV SPECTROSCOPY

6. ATOMIC EMISSION SPECTROSCOPY (AES)

o Principle
o Advantages
o Disadvantages
o Applications

7. ATOMIC ABSORPTION SPECTROSCOPY (AAS)

o Principle
o Application

8. TYPES OF SPECTRUM

o Continuous Emission Spectrum

o Line or Atomic Emission Spectrum
 Features of Line Spectrum
 Line Spectrum of Hydrogen

9. MASS SPECTROMETRY (MS)

o Principle
o Instrumentation And Working

10. CONCLUSION

11. REFRENCES
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INTRODUCTION

Spectroscopy is a branch of science concerned with the spectra of

electromagnetic radiation (EMR) as a function of its wavelength or frequency
measured by spectrographic equipment, and other techniques, in order to
obtain information concerning the structure and properties of matter. Spectral
measurement devices are referred to as spectrometers, spectrophotometers,
spectrographs or spectral analyzers.
Spectroscopy as a science began with Isaac Newton splitting light with a
prism and was called optics. Therefore, it was originally the study of visible
light which we call color that later under the studies of James Clerk Maxwell
came to include the entire electromagnetic spectrum. Although color is
involved in spectroscopy, it is not equated with the color of elements or
objects which involve the absorption and reflection of certain electromagnetic
waves to give objects a sense of color to our eyes. Rather spectroscopy
involves the splitting of light by a prism, diffraction grating, or similar
instrument, to give off a particular discrete line pattern called a “spectrum”
unique to each different type of element.
Spectroscopic studies were central to the development of quantum mechanics,
because the first useful atomic models described the spectra of Hydrogen
which models include the Bohr model, the Schrödinger equation, and Matrix
mechanics which all can produce the spectral lines of Hydrogen. Also, Max
Planck's explanation of blackbody radiation involved spectroscopy because
he was comparing the wavelength of light using a photometer to the
temperature of a Black Body. Spectroscopy is used in physical and analytical
chemistry because atoms and molecules have unique spectra.
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ELECTROMAGNETIC RADIATION (EMR)

 Electromagnetic Radiation is the form of radiation energy such as light

energy.
 Electromagnetic Radiation has the properties of both a wave and a particle
like discrete packet of energy called quanta or photons.

CHARACTERISTICS :~

Wavelength – The distance between two successive crests or troughs of a wave in a

beam of radiation is called wavelength λ. Its units are Å, nm and m. (1m = 109 nm =
10
10 Å)

Frequency – The no. of waves passing through a point on the path of a beam of
radiation per second is called frequency. Its unit is Hertz (Hz) or cycles per second
(cps). (1 cps = 1 Hz)

Wave Number – It is the no. or waves passing per centimeter. A common unit of
wave number in 1cm-1.

Energy- EMR can be characterized in terms of energy possessed by each photon of

radiation. The SI unit is joule (J). Each photon has an energy which is proportional to
the frequency of light.
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SPECTROPHOTOMETER

 The instrument used to measure the amount of EMR absorbed by a compound

is called spectrophotometer or spectrometer.

 It consists of a light source of radiation, a prism that can select the desired
wavelengths which are passed through a sample of the compound being
investigated.

 The radiation that is absorbed by the sample is detected and is recorded on a

chart against the wavelength or wave number.

 Absorption peaks are plotted as minima in Infrared Spectroscopy and usually

as maxima in UV Spectroscopy.

CHARACTERISTICS :~

1. Determines how much light is reflected by a chemical.

2. Measures the strength of light as a light beam travels through a sample solution.

3. Objective calculation of visible light, UV light or infrared light emissions or

reflection.

EXAMPLES :~

1. Single & Double Beam Spectrophotometer

2. Based on Light Wavelength (UV, Visible, Infrared)

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INFRARED SPECTROSCOPY (IR)

 Wavelengths in IR region extends from 2.5 to 16 μm (4000 – 625cm-1)
 IR is weak energy radiation but it does supply sufficient energy for bonds in
the molecule to vibrate.
 The molecular motion that is affected by the absorption of quanta of the IR
radiation is the vibrational motion.
 The studies of vibrational spectra of molecules lead to information of the
flexibility of molecules.

EFFECTS OF IR ON MOLECULES :~

1. The small displacement of the constituents atoms from their equilibrium positions
can be seen in term of vibrational motion of atoms.

2. Such changes in the bond length produce a change in the dipole moment of a
heteronuclear molecule and if the oscillating dipole couples with the electrical field of
the radiation, an exchange of energy takes place.
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VISIBLE & UV SPECTROSCOPY

 In UV – Visible Spectroscopy, the absorption of UV (200-400nm) and Visible

(400-800nm) radiation by molecule is associated with the extraction of loosely
held electrons (such as unshared electrons in a π bond) from a lower energy
occupied molecular orbital (MO) to a higher energy unoccupied molecular
orbital (MO*).
 There are three types of electrons – Electrons in sigma bond σ, Electrons in pi
bond π, Unshared electrons n
 On absorbing energy any of these electrons can enter excited state which are
either non bonding σ* or π* orbitals.
 Only the n < π*, π < π* and more rarely the n < σ* excitations occur in the near
UV and visible region.
 The energy required for σ < σ* transition is very high and therefore it occurs in
vacuum UV region (below 200 nm).
 The relative energy for 3 electrons transition detectable by UV spectrometer
in order of increasing △E is :
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ATOMIC EMISSION SPECTROSCOPY (AES)

 AES pertains to electronic transitions in atoms which use an excitation source

like flame sparks.
 ES is concerned with the characteristics radiation produced when atoms are
excited.
 They emit radiations in the form of discrete wavelengths of light, called
spectral lines while returning to the lower energy states.

.PRINCIPLES :~

1. The source vaporizes the sample and cause electronic excitation of elementary
particles in the gas.

2. Exited molecules in the gas phase emit band spectra.

3. Thus, a molecule is in an excited state of energy, E2 undergoes a transition to a

state of lower energy E1 and a photon of energy hv is emitted where,

E2 – E1 = hv

4. In each electronic state a molecule may exist in a number of vibrational and

rotational states of different energy.

ADVANTAGES :~

1. Highly specific.

2. Extremely sensitive. Detection is possible even in low concentration.

3. Even metalloids have been identified by this technique.

4. Can be performed on solids and liquids with equal convenience.

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5. Minimum sample is required.

6. Rapid results , automated machines give results in just 30 sec.

7. Used for a wide variety of sample.

DISADVANTAGES :~

1. Costly and wide experience is required.

2. Recording is done on a photographic plate which takes some time to develop, print
and interpret the results.

3. Radiation intensities are not always reproducible.

4. The accuracy and precision are not high.

APPLICATIONS :~

1. ES has been employed in determining the impurities of Ni, Mn, Cr, Si, Al, Mg,
As, Sn, Co, V, Pb, Bi, P and Mo in iron and steel in metallurgical process.

2. Alloys of Zn, Cu, Pb, Al, Mg and Sn have been analyzed.

3. Lubricants oils have been analyzed for Ni, Fe, Cr, Mn, Si, Al and so on. If the
concentration of metal in lubricating oil has been increased during use, it indicates
excessive wear and tear need for engine overhaul.

4. In petroleum industry oil is analyzed for V, Ni, Fe the presence of which makes
fuel poor. ES has been used to detect 40 elements in plants and soil.

5. Solid samples and animal tissues have been analyzed for several elements
including K, Na, Ca, Zn, Ni, Fe and Mg etc.

6. The following materials have been analyzed by AES :- Ceramics; Co, Ni, Mo and
V in graphite; Trace metals impurities in analytical reagent.
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ATOMIC ABSORPTION SPECTROSCOPY (AAS)

 This technique is particularly useful in the determination of trace metals in

liquids.
 60 – 70 elements have been analyzed by this technique in concentration as
low as 1 ppm.
 AAS can be useful for the analysis of one metal in the presence of another
metal, thus it is time saving and eliminating error.

.PRINCIPLES :~

1. When white light is allowed to pass a sample of a substance, it may absorb

radiation of a particular wavelength.

2. There will be a dark space in the continuous spectrum of white light for that
particular wavelength.

3. A substance which absorbed a particular radiation in normal state will emit the
radiation in excited state.

4. The emission lines and absorption lines will be exactly at the same place in the
spectrum.

APPLICATIONS :~

1. Well suited for the analysis of a substance at low concentration. It has several
advantages over AES.

2. Highly specific technique. Analysis of a metal from a complex mixture is possible

and a high energy source needs not to be employed.

3. Used for analysis of ceramics, mineralogy, biochemistry, metallurgy, water

supplies and soil analysis.
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TYPES OF SPECTRUM

1. CONTINUOUS EMISSION SPECTRUM

2. LINE OR ATOMIC EMISSION SPECTRUM

CONTINUOUS EMISSION SPECTRUM

 When a narrow beam of white light is passed through a prism, it spreads out
into a band of seven colors on the screen.
 The seven colors diffuse into each other.
 The boundary lines between the colors cannot be marked.

LINE OR ATOMIC EMISSION SPECTRUM

 When an element is vaporized in a flame, or in an electric arc or in a discharge

tube, it emits a light of characteristic color.
 The resolution of ray of this light produces colored lines separated by dark
spaces.
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FEATURES OF LINE SPECTRUM :~

 Each elements has its own characteristics color by which it can be identified
i.e.
 Na gives yellow color in Bunsen flame
 Sr gives red color in Bunsen flame
 Al gives violet color in Bunsen flame
 Similarly in a discharge tube :
 Ne glows with orange red color
 He glows with orange pink color
 H2 glows with orange red and blue color
 Cl2 glows with orange green color
 The lines in the spectrum of an element are not haphazardly distributed but
they occur in groups or series. In series the separation between them decreases
regularly as their wave length decreases. At a certain limiting value, the
spectrum becomes continuous.

LINE SPECTRUM OF HYDROGEN :~

 H2 gives red color spectrum in excited state.

 In normal state it absorbs the red color.

 Thus, there will be a dark line in place of red color in the continuous spectrum
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MASS SPECTROMETRY (MS)

 The mass spectrometer is an instrument which turns atoms and molecules into
ions and measure their mass.
 Mass spectrometry is a technique which involves the production of gaseous
ions from the sample, their separation according to their mass to charge ratio
(m/e) and the measurement of the relative abundance of these ions.
 This technique is called spectrometry and not spectroscopy bcause no
absorption of light is involved.

.PRINCIPLES :~

 In mass spectrometry, as organic molecule under high vacuum is bombarded

with an electron of energy greater than the molecule, (around 10 ev mostly).

 As a result of this, one of the electron of the molecule is dislodge and a singly
charged molecular ion is produced.

 The molecular ion produced in this primary process, is a radical cation, i.e. it
has unpaired electron and positive charge.

M + e- = M+ + 2e-

 The sample in the vapor phase is subjected to a beam of electrons of 70 eV

energy.
 These highly eergetic electrons ionize the organic molecules and also imparts
a large amount of energy to the molecular ions.
 A molecular ion is generally dissociated into fragments called Fragment ions.
M. + = (m1+ + m2) or (m1+ +m2 )
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 The positively charged iond are separated by deflection in a variable magnetic

field.
 The ions are directed into an analyzer tube surrounded by a magnet.
 The magnet deflects the ions from their original path causing them to adopt a
circular path the radius of which depends upon the m/z ratio of the ions.
 The ion beam of a particular m/z can be selectively focused through a narrow
slit into an ion collector where it generates a current proportional to the
relative abundance of the ions in the beam.
 The mass spectrum I a plot of relative intensity of the ions against their
dimensionless m/z value.
 The doubly charged ions are deflected much more than singly charged ions
and appear in the mass spectrum at half the m/z value (m/2z) of the singly
charged ion of the same mass.
 For example a doubly charged ion of mass 90 give rise to a peak at m/z 45.

.I NSTRUMENTATION AND WORKING:~

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There are 5 main stages :

1. Vaporisation – The sample is turned into a gas using an electrical heater.

2. Ionisation – The gas particles are bombarded with high energy electrons to
ionize them. Electrons are knocked off the particles leaving positive ions.

3. Acceleration – The positive ions are accelerated by an electric field.

4. Deflection – The positive ions paths are altered with a magnetic field. Lighter
ions have less momentum and are deflected more than heavier ions. For a given field,
only ions with a particular mass/charge ratio will make it to the detector.

5. Detection – The magnetic field strength is slowly increased. This changes the
mass charge ration of ions that can reach the detector. A mass spectrum is produced.
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CONCLUSIONS
 Spectroscopy is used as a tool for studying the structures of atoms and
molecules. The large number of wavelengths emitted by these systems makes
it possible to investigate their structures in detail, including the electron
configurations of ground and various excited states.

 Spectroscopy also provides a precise analytical method for finding the

constituents in material having unknown chemical composition. In a typical
spectroscopic analysis, a concentration of a few parts per million of a trace
element in a material can be detected through its emission spectrum.
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REFRENCES

 https://en.wikipedia.org
 https://www.slideshare.net
 https://www.cram.com
 https://www.britannica.com
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THANK YOU