• Spectroscopic methods of analysis – Introduction to spectroscopy – Energy concepts, properties

of EMR, General features of spectroscopy, Types of molecular spectra, Interaction of EMR with
matter, Instrumentation, Applications
6
• Microwave spectroscopy – Introduction, Diatomic rigid rotor model, Non-rigid diatomic
molecules, Instrumentation, Applications, Advantages and disadvantages
4
• Raman spectroscopy – Basic principles, Properties of Raman lines, Mechanism of Raman effect-
Classical and quantum theories, Techniques and instrumentation, Applications
2
• Infrared spectroscopy – Background and theory, Diatomic molecule as a harmonic oscillator,
Numerical problems, Diatomic molecule as anharmonic oscillator, Diatomic vibrating rotator,
Vibrations of polyatomic molecules, Instrumentation and techniques of dispersive and FT-IR,
Double beam IR spectrometer, Uses of IR spectrum, Advantages and limitations 5

• UV-visible spectroscopy – Theory of electronic spectra of diatomic molecules, Types of transitions

in organic molecules, Instrumentation, Double beam spectrophotometer, Applications in
qualitative and quantitative analysis, Spectrophotometry, Beer’s law and its derivation, Deviations
from Beer’s Law, Numerical problems 5
• NMR spectroscopy – Basic principles of NMR, Chemical shift, Spin-spin coupling, Instrumentation,
Applications of proton NMR spectroscopy 3
• Chromatographic Techniques – General concepts, Classification, Column chromatography, HPLC,
Instrumentation, Applications, Thin layer chromatography, Experimental techniques, Applications,
Advantages and disadvantages, Gas chromatography, principles, instrumentation and applications
9
• Electroanalytical methods- Conductometric titrations – basic principles, Applications in titrations
involving weak and strong acids and bases, Potentiometric titrations- Fundamental principles,
 Chemical Analysis
The resolution of a chemical compound into its
proximate or ultimate parts; the determination
of its elements or of the foreign substances it
may contain.
 Chemical analysis

Qualitative analysis Quantitative analysis

 Qualitative vs. Quatitative Analysis
Tells about the quality or • Tells about the quantity
number of elements of the substance or the
present element present

It does not involve any • involves measurements

measurement and and statistics
statistics
• It is used to quantify
It is used to gain an attitudes, opinions,
understanding of behaviors, and other
underlying reasons, defined variables
opinions, and motivations
In general the analysis can be carried out using different
techniques/methods as follows:
1. Common methods of analysis: Wet methods like titrimetry and
gravimetry, voltammetry, coulometry, potentiometry and
conductometry
2. Instrumental techniques: spectroscopy, electrochemistry and
chromatography
3. Special techniques:
X-ray method
Methods based upon the measurement of radioactivity
Mass spectrometry
kinetic methods
and thermal methods
 Spectroscopy
Spectroscopy is a branch of science dealing with the
study of interaction of electromagnetic radiation with
matter

The most important consequence of such interaction is

that energy is absorbed or emitted by the matter in
discrete amounts called quanta

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 samples.
The study of spectroscopy can be carried out under the following
heads:

1. Atomic spectroscopy:

 This deals with the interaction of electromagnetic radiations with

atoms which are most commonly in their lowest energy state
called the ground state.

 Monoatomic substances normally exist in the gaseous state and

are able to absorb electromagnetic radiation, resulting in
transitions of electrons from one electronic energy level to
another
ΔE = h ν
 Its importance has increased by the development of lasers
2.Molecular spectroscopy
This deals with the interaction of EMR with
molecules results in transitions between
rotational and vibrational energy levels in
addition to electronic transition.

The spectra of molecules are much more

complicated than those of atoms
Atomic Spectroscopy Molecular Spectroscopy

1. Concerns only the properties of atoms. 1. Molecular spectroscopy concerns the

molecules which are infinitely more
2. It involves only electronic transition numerous.
2. It involves electronic, vibrational and
3. With atomic spectroscopy you can rotational transitions
found the nature and the amounts of a 3. Molecular spectroscopy concerns all the
given element in your sample interaction of electromagnetic waves
with the matter and gives us much more
advice than atomic spectroscopy
especially about chemical functions,
structure of matter
4. It yields line spectrum 4. It yields band spectrum

5. Easy to interpret 5. Difficult to interpret

 Why the name Electromagnetic spectrum?

• Visible light is a form of energy, which can be described by

two complementary theories: the wave theory and the
corpuscular theory. Neither of these theories alone can
completely account for all the properties of light: some
properties are best explained by the wave theory and others
by the corpuscular theory. The wave theory says that the
propagation of light by light waves involves both electric and
magnetic forces,which give rise the name Electromagnetic
radiation
 Y

Electronic
vector
Wavelength
λ Electronic
component

X Direction of
propagation

Z
Magnetic component

Representation of Electromagnetic Wave

 EM Spectrum
• Diagram
The full width at half maximum
 Consequences of Interaction of EMR with
matter
1. Absorption of Radiation. If the photons of radiation possess
the appropriate energies, they may be absorbed by the
matter and result in electronic transitions, vibrational
changes or rotational changes or combinations of these.
After absorption, atoms and molecules become excited.
They give out energy quickly either by losing energy in the
form of heat or by re-emitting electromagnetic radiation.
Examples: Microwave, UV-Visible, IR . X-ray etc.,
2. Scattering and reflection of Radiation. The portion of EMR
may undergo scattering or reflection or may be re-emitted at
the same wavelength or a different wavelength. Example:
Raman spectroscopy.
3. Polarization of radiation: EMR is neither
absorbed nor scattered, it may undergo
changes orientation or polarisation. Example. Polarimeter
4. Emission and fluorescence of radiation. In some cases , the
molecules after absorbing radiation become excited but they
do not lose energy very quickly but with some delay. In such
cases the energy is re-emitted as radiation, usually of longer
wavelength than was originally absorbed. This phenomenon
is known as fluorescence (quick re-emission) and
phosphorescence (delayed re-emission)
5. Refraction and Diffraction of radiation: Example
Refractometer, x-ray etc.,
 Terms used in spectroscopy

• Wave length: It is the distance between two successive maxima

on an electromagnetic wave. It is denoted by Greek Letter λ

• Frequency: The number of wavelength units passing through a

given point in unit time is called the frequency of radiation. It is
denoted by Greek letter ,ν

• Wave number: The number of waves per centimeter in vacuum,

denoted by ν
• Radiant Power and Intensity: The radiant power P in watts (W)
is the energy of a beam that reaches a given area per unit time.
The intensity is the radiant power per unit solid angle. Both
quantities are proportional to the square of the amplitude of
the electric field. Although it is not strictly correct, “ radiant
power and “ intensity” are frequently used interchangeably
 Units
Wavelength: Meters
commonly in nanometers (1 nm = 10-9 meters)
Angstroms still used
Named for Swedish Astronomer who first named these
wavelengths
1 nanometer = 10 Ao
1 μ m = 10 -6 m =10-4 cm =10+3 nm
Frequency in reciprocal seconds, s-1 or hertz (1 s-1= 1 hertz)
1 Hz = 1 cycle/s ; 1 Fresnel = 1012 Hz ; 1MHz = 10 3 kHz =106 Hz
Wave number in reciprocal meters, m-1 ; cm-1 = Kayser (K) ,
kK=kilokayser → 1kK= 1000cm-1

Energy in joules, J

Velocity : V = Frequency x λ
cm/s ; m/s
Relation between frequency, Velocity and Wave number
ν = c/λ
Wave number = ν /c
 Numericals
1. Calculate the energy in Joules per quantum, calories per mole and
electron volts of photons of wavelength 3000 Aº
Solution : 6.62 x 10 -34 J.s x 3 x 108 m s-1
E= hν = h c /λ =
3000 x 10-10 m
= 6.62 x 10 -19 Joule
Energy per mole = Nhν = (6.02 x 1023 mol-1) x( 6.62 x 10 -19 Joule)
= 3.98 X 105 Joule/mol
3.98 X 105 Joule/mol
Calories per mole = = 95,300 cal mol -1
4.184 Joule/cal
95,300 cal mol-1
Ev of photons =
23, 060 cal mol-1 eV-1
= 4.13 eV
2. Calculate ν, ν and E for typical ultraviolet radiation of
wavelength 2000 A
6.62 x 10-27erg.s x 3 x 10 10cm s-1
Solution: E= hν = h c /λ =
2000 x10 -8 cm
= 9.93 x 10 -12 erg

ν = c /λ = 3 x 1010 cm s-1 / 2000 x 10-8 cm = 1.5 x1015 cycles. s-1

ν= 1/ λ = ν/ c = 1.5 x1015cycles.s-1 = 5 x 104 cm-1

3 x 1010 cm s-1
3. For infrared radiation of 5μm, what is the wave number in cm-1 ?
Solution. Wave number = ν= 1/ λ
= 1/ (5 x10-4 cm )=2000 cm-1

4. Calculate the energy in joules of one photon of the radiation with a wave
2000 cm-1.

E = hcν = 6.626 x 10-34 J.s x 3 x 1010 c m s-1 x 2000 cm-1

= 3.98 x 10-20 J