UNIT III PHOTOCHEMISTRY AND SPECTROSCOPY

Photochemistry: Laws of photochemistry - Grotthuss–Draper law, Stark–Einstein law and Lambert-Beer Law.
Photoprocesses - Internal Conversion, Inter-system crossing, Fluorescence, Phosphorescence,
Chemiluminescence and Photo-sensitisation. Spectroscopy: Electromagnetic spectrum - Absorption of radiation –
Electronic, Vibrational and rotational transitions. Width and intensities of spectral lines. Spectrophotometric
estimation of iron. UV-visible and IR spectroscopy – principles, instrumentation (Block diagram) and applications

PHOTOCHEMISTRY

It is the study of the interaction of electromagnetic radiation with matter resulting into a physical change or into a
chemical reaction. The primary step in any photochemical process is the absorption of energy by an electron:

A + hν A*. This excitation can take place with or without a change in the spin state of the electrons.

SINGLET AND TRIPLET STATES

PAULI EXCLUSION PRINCIPLE: “no
excited two electrons in an atom can have
singlet state the same set of 4 quantum
Excited triplet state is of less numbers”, in other words:
energy than excited singlet two electrons in the same orbital
state. must have opposite spins (we say:
Singlet to triplet transitions they are "paired": no net magnetic
are far less probable than
field = the molecule will be
singlet/singlet transitions.
"diamagnetic"), molecule with
excited unpaired electrons (e.g. triplet
triplet state state) possess magnetic moment,
are attracted by magnetic field,
are called "paramagnetic"
ground state

ELECTRONIC AND VIBRATIONAL LEVELS

➢ S0: ground state of a molecule at ambient temperature

➢ S1 and S2: excited singlet states

➢ T1: lowest energetic triplet state, usually of less energy

than lowest energetic excited singlet state S1.
Same E
S1

T1

Because Singlet / triplet transitions are less probable than singlet /

singlet transition (because spin conversion is necessary) ,
thus the average lifetime of an excited triplet state is 10-4 sec and
more, while excited singlet state lifetime is 10-8 to 10-5 s.
When a molecule is excited into an electronically excited state by absorption of a photon, it can undergo different
processes – 1. Photophysical processes and 2. Photochemical processes.

• Photophysical processes include radiative and non-radiative transitions.

• In radiative transitions, the excited molecule emits light in the form of fluorescence or
phosphorescence and returns to the ground state. Examples: luminescent screens for x-ray and
television, fluorescent lamps, optical brighteners in paints and white dress materials.

• In non-radiative transitions, some or all of the energy of the absorbed photon is ultimately converted
to heat. Non-radiative processes are : Internal conversion, Inter-system crossing and vibrational
relaxations.

• Photochemical processes are those in which the excited species dissociates, isomerizes, rearranges, or react
with another molecule. Photochemical processes are: Photosynthesis, vision, photolithography, manufacture
of PCBs.

Laws governing absorption of light:

▪ Lambert’s Law: This law states that decrease in the intensity of monochromatic light with the thickness of
the absorbing medium is proportional to the intensity of incident light.

-dI/dx α I or -dI/dx=KI, which on integration changes to: I=I0 e-Kx

where I 0 = intensity of incident light, I=intensity of transmitted light & K= absorption coefficient.

▪ Beer’s Law : It states that decrease in the intensity of monochromatic light with the thickness of the solution
is not only proportional to the intensity of the incident light but also to the concentration ‘c’ of the solution.
Mathematically, -dI/dx α Ic

or -dI/dx = ЄIc ,which on integration changes to I=I0 e- ЄCx

where, Є = molar absorption coefficient or molar extinction coefficient.

The two are combined and expressed as Beer-Lambert’s law: log I0/I =  c x , where I0 and I represent the intensities
of incident light and transmitted light respectively,  is absorptivity or coefficient of absorption, c is the concentration
of absorbing species and x is thickness of the absorbing medium or path length.

Laws of photochemistry:
1. Grotthus-Draper Law: The first law known as Grotthus-Draper law states that only that light which is
absorbed by a system can cause chemical change.

2. Stark-Einstein law: The second law of photochemistry called Stark-Einstein law is also known as the law
of photochemical equivalence. The law states that one quantum of light is absorbed per molecule of
absorbing and reacting substance that disappears. The energy absorbed by one mole of the reacting
molecules is given by E=Nhν. This energy is called one einstein.

hν
A A* photoproducts
Quantum efficiency or quantum yield of a reaction

Einstein’s Equivalency Principle

One particle of a chemical substance can absorb
only one photon from a light beam: DE = hn

E = hn = h c
l
h = Planck’s constant (6.6 x 10-34 Js)
c = speed of light (3 x 108 ms-1)
l = wavelength
n = frequency

For one mole: DE = Nhn

The efficiency of a photochemical reaction is expressed in terms of quantum efficiency or quantum yield, first
introduced by Einstein. The quantum yield  is defined as the ratio of number of molecules decomposed or formed
to that of number of quanta of light absorbed.

No. of molecules formed or decomposed

Quantum yield =  = ----------------------------------------------------
No. of quanta of light absorbed

Experimentally,
Ф= rate of chemical reaction
quanta absorbed per second.

The observed  values for different reactions vary from a very low fraction of unity to a very high value of a million
because of the complexity of photochemical reactions.
 Photophysical processes of deactivation of excited stated molecules:
Jablonsi diagram

➢ The excited state atom or molecule is formed by absorption of light which occurs over a time span of about
10-15 second. The excited state molecule has a life time of about 10-9 second and relaxes to the ground state
by a variety of pathways.
➢ The photophysical pathways of relaxation include (i) non-radiative as well as (ii) radiative pathways. The
non-radiative pathways include internal conversion (IC) and vibrational relaxation (VR) through which the
excited state molecule loses the energy gained by absorption of light shown as dotted lines in the following
Jablonski diagram:

S2
IC Excited state electronic energy levels

ISC
Energy VR VR
S1
reverse ISC T1 (Triplet energy state)
A F P
IC

Vibrational energy levels

S0 Ground state electronic energy

level

Jablonski diagram indicating electronic and vibrational energy levels in a molecule, the processes of
absorption and photophysical pathways of relaxation of excited state molecules.

A – absorption; F- fluorescence; IC-internal conversion; ISC-intersystem crossing; P-phosphorescence; VR-

vibrational relaxation; S0- ground state electronic energy level; S1 and S2 –excited state electronic energy levels;
T1 – first excited triplet state; v and v’- vibrational energy levels.

Non-radiative photophysical processes:

1. In internal conversion (IC) an excited state electron passes from a low vibration level of S2 to an equally
energetic vibration level of the S1. The molecule in the S1 state also may relax to the ground state S0 by internal
conversion. The vibrational relaxation involves the loss of vibration energy of the excited state molecule in
the form of heat by collision with solvent molecules. Life span of the IC pathway is about 10-12 second.
2. In Intersystem crossing (ISC) an electron in the excited state molecule reverses its spin. This corresponds
to a spin multiplicity of 3 and the excited state molecule goes over to a triplet state, T1. The triplet state T1 is
lower in energy than the corresponding single state S 1. A similar reverse intersystem crossing ISC can take
place between the lower vibrational energy levels of T1 to equivalent vibrational energy levels of S0.

Radiative photophysical processes:

The radiative pathways by which an excited state molecule relaxes to the ground state include emission of
fluorescence (F) and phosphorescence (P).
 1. Fluorescence:
a. Fluorescence emission occurs when the relaxation from S1 to S0 state occurs with emission of light.
b. It is a spin allowed transition and occurs rapidly, within 10-7 to 10-9 second.
c. The emitted photon has a longer wave length than the absorbed photon.
d. It is usually shown by flat, rigid molecules with extensive conjugation and delocalization.
2. Phosphorescence:
a. After intersystem crossing from singlet to triplet state, the molecule in the triplet state relaxes to the
lowest vibrational state of T1 by vibrational relaxation. When the deactivation from T1 to S0 occurs
by emission of a photon, this process is called phosphorescence.
b. Electronic transitions between states of different multiplicities are forbidden quantum mechanically
and hence the intensity of phosphorescence is weak compared to that of fluorescence.
c. The life time of a triplet state is much longer and hence phosphorescence emission can be observed
over a time span of 10-3 to 10 seconds even after the removal of the excitation source.
d. Usually observed at low temperatures in highly viscous media.

Photochemical reactions
Photochemical reactions involve a two step process, (i) a primary process and (ii) a secondary process. The
primary process involves the formation of active species either by absorption of light or by photodissociation to form
free radicals after absorption of light.
M + hν M* (activated molecule)

Or AB + hν A + B (free radical)

The secondary process involves the reaction of the activated molecule or free radical to form products. In many
reactions the quantum yield is quite low as all the activated molecules may not participate in the chemical
transformation but undergo deactivation by photophysical processes. In the case of reactions involving free radicals
the φ value may be quite high due to secondary processes involving thermal or dark reactions.

Organic molecules undergo photochemical reactions due to electronic transitions of π π* or n π* or

intra-molecular charge transfer excitation. The different types of photochemical reactions of organic molecules may
be classified into (i) isomerization (ii) fragmentation (iii) simple addition and cycloaddition (iv) substitution (v)
oxidation – reduction and (vi) electron transfer reactions.

Chemiluminescence
i) It is defined as the production of light by chemical reactions. This is the most common form of
luminescence in living organisms.
ii) The chemical reaction liberates sufficient energy to electronically excite at least one species in the reaction
mixture and promote it to an excited state.
iii) The excited species then relaxes by emission of radiation.
iv) A+B C + D + energy
C + energy C*S1
*
C S1 C S0 + hν
*

Examples:
i) Insects like fireflies use chemiluminescence to attract their mates. In fire flies, luciferon is
converted to luciferin by luciferase enzyme. Luciferin emits bioluminescence.
ii) Deep sea fish like the Anglerfish use it to lure prey close to their mouth.
iii) Microorganisms use it to signal distress.
iv) Glow of phosphorous and its oxides.

v) Chemiluminescence has been observed in oxidation reactions of hydrazides (e.g. luminol or 3-

amino cyclicphthalhydrazide) and decomposition of oxetanes.
 Photosensitisation
It involves the excitation of a molecule called donor molecule or sensitizer which then transfers the energy to another
molecule called acceptor molecule. The acceptor molecule then undergoes a physical or chemical transformation.
Mechanism:
i) The donor molecule (D) can be easily excited by the absorption of radiation : D + hν D*
ii) Acceptor molecule then accepts the excess energy from the excited donor : D * + A D + A*

For the photosensitization to be effective, the transfer of energy from D* to A should occur before it starts
loosing the energy through photophysical pathways.
iii) Molecule A* can then under go physical or chemical changes.

Examples:
1. Photosynthesis is a typical example of photosensitized reaction. Chlorophyll, the green pigment in plants,
absorbs in the 400-700 nm region of sunlight and sensitizes the reaction between carbon dioxide and water to
form carbohydrates.
hn; chlorophyll
6CO2 + 6H2O C6H12O6+6O2
several steps
carbohydrate
1. Chlorophyll acts as a catalyst absorbing and
transferring the photon energy for reduction of
carbon dioxide to carbohydrate

2. This reaction maintains the life on the Earth:

CO2; H2O carbohydrate

sunlight

Fossil energy Food

(coal, oil, natural gas)

2. Mercury vapour sensitizes the decomposition of water, ammonia, ethanol and acetone.
3. Many organic syntheses use benzophenone as a sensitizer.
4. Photocatalytic degradation of organic compounds in the presence of semiconductor oxides like TiO 2, ZnO.
5. Photograph development – Dyes are used as sensitisers to activate AgBr.

Photoquenching:

When two or more excited molecules collide with each other in the excited state, they loose their energy, wth or
without the formation of products. This is called as photoquenching.

SPECTROSCOPY
Spectroscopy deals with the transitions induced in a chemical species by its interactions with the photons of
electromagnetic radiation.

Spectroscopic methods are generally used to measure the energy difference between various molecular energy levels
and to determine the atomic and molecular structures.

Electromagnetic radiation:

• Light or electromagnetic radiation is a form of energy that is transmitted through space at a constant velocity
of 3 x 108 m s-1.
• These radiations are said to have dual nature exhibiting both wave and particle characteristics.
• The dual character is indeed useful for understanding the interactions of radiations with matter.

Wave theory of electromagnetic radiations:

• According to this theory, the electromagnetic radiations travel in the form of waves.
• This wave motion consists of oscillating electric and magnetic fields (vectors) directed perpendicular to each
other and perpendicular to the direction of the propagation of the wave as shown in the Figure 1.
• They do not require any supporting medium for transmission.

Figure 1

• In the spectroscopic studies, the effects associated with the electrical component of the electromagnetic wave
are important.
• The propagation of vibrations in the electric field only is exhibited in the Figure 2.

Figure 2: The electric component of a propagating light wave

Wave Parameters:
i) Wave length (λ):
 • Distance between the peaks of the waves.
• It is expressed in terms of centimeter (cm), metre (m), micron (µ) or micrometer (µm), or
angstrom (Å) units.
ii) Frequency (ν):
• Number of cycles per second.
• Wavelength and frequency are related to each other by the relationship

Frequency (ν) = Speed of light in cm/sec

Wavelength in cm/sec
i.e., ν = c/ λ
• It is measured as cycles per second (cps) called Hertz (Hz).
iii) Wavenumber
• This is the reciprocal of wavelength, i.e., the number of wavelengths per centimetre. It is
denoted by the symbol v¯ (nu bar).

• It is expressed in cm–1 or m–1.

iv) Power: Energy per unit time.

v) Energy of a photon:
The energy E of the photon is propotional to the frequency of radiation and is given by the euation
E = hν
Where h is planck’s constant [6.625 x 10-27 erg second]
E = hc/λ = hcν-
The electromagnetic spectrum:
• For most spectroscopic purposes, it is considered to be consisting of the region of radiant energy ranging
from wavelengths of 10 metres to 1x10-12 centimetres.
• When a molecule absorbs electromagnetic radiation, it can undergo various types of excitation.
• This excitation may be electronic excitation, rotational excitation, excitation leading to a change in nuclear
spin, excitation resulting in bond deformation and so on.

Regions of electromagnetic spectrum:

Radiowave Microwave Infrared Visible Ultraviolet X-Rays γ-Rays Cosmic rays

Spectroscopy:
1. Study of interaction of electromagnetic radiation with matter.
2. Analytical tool for the study of atomic and molecule structures.
3. Most useful regions – Microwave, IR, Visible and UV.
4. Based on Interaction it is classified in to Atomic spectroscopy and Molecular spectroscopy.
5. Atomic spectroscopy: Interaction of emr with ground state atom.
Molecular spectroscopy: Interaction of emr with molecules.

Absorption and emission of Electromagnetic radiation:

➢ If a photon of frequency ν falls on a molecule in the ground state, and if its energy hν is equal to (or) greater
than the difference in the two molecular energy levels, then, the molecule undergoes a transition from lower
to higher energy level with the absorption of photon of energy hν, it is referred to as absorption (a) and the
spectrum obtained is absorption spectrum.
➢ If the molecule falls from excited state to lower energy state with the emission of photon of energy hν, it is
referred to as emission (b) and the spectrum obtained is emission spectrum.
The Energy levels for electrons in a molecule:
• The energy levels can be rated in the following order
Electronic > Vibrational > Rotational.
• Each of these transitions differs by an order of magnitude.
• Rotational transitions occur at lower energies (longer wavelengths) and this energy is insufficient and cannot
cause vibrational and electronic transition.
• Vibrational (near infra-red) and electronic transitions (ultraviolet region of the electromagentic spectrum)
require higher energies.
• The diagram below illustrates possible transitions that occur. A , represents pure rotational changes (far
infared).B, rotational -vibrational transitions; C, rotational-vibrational-electronic transitions(visible and
ultraviolet) Eo is electronic ground state and E1 is the electronic excited state.

The various regions of electromagnetic spectrum are set out in Table 1 and are labeled according to the type of
transitions and type of spectroscopy involved.

Radiation Type of transition Type of Spectroscopy Wavelength

(centimeters)
 • Radio Magnetically induced spin Nuclear Magnetic
> 10
Resonance (NMR)
• Microwave Molecular rotation Microwave absorption
10 - 0.01
spectroscopy
• Infrared Molecular vibration IR and Raman 0.01 - 7 x 10-5
• Visible Electronic transition Absorption, Emission
involving outershell and fluorescence 7 x 10-5 - 4 x 10-5
electrons spectroscopy
• Ultraviolet Electronic transition Uv absorption
4 x 10-5 - 10-7
spectroscopy
• X-Rays Inner shell electrons X-ray absorption and
10-7 - 10-9
emission spectroscopy
• Gamma Rays Nuclear Emission spectroscopy < 10-9

Spectra: It consists of number of lines and peaks. Each one is associated with height and width. (Height → Intensity)

I. Factors influencing the intensity of spectral peaks:

➢ Number of lines/peaks and intensity depend on:
1.Magnitude of individual transition probabilities (i.e.,)Selection rule:
Selection rule determines whether a particular transition is allowed or forbidden.
Allowed transition – Spectral lines of greater intensity.
Forbidden transition – Spectral lines of lower intensity.

Selection rule for:

i. Rotational transitions: ΔJ = ± 1
ii. Vibrational transitions: ΔV = ± 1 and ΔJ = ± 1
2. Relative population of energy levels between which transitions occur:
Boltzmann distribution:
(Nupper / Nlower )= e (-ΔE/kT)

where Nupper – number of molecules in the upper energy level.

Nlower – number of molecules in the lower energy level.
ΔE - energy difference between the levels
k - Boltzmann constant (1.38 x 10 -23 J/K)
3. Concentration (or) path length of the sample:
Example: Beer-Lambert’s law.
A=εbc
where A - absorbance
ε - molar absorbtivity with units of L mol-1cm-1
b - path length of the sample (cuvette)
c - Concentration of the compound in solution, mol L-1
II. Factors influencing the width of the spectral peaks:

➢ Width of the spectral line depends on:

1. Natural line width of atomic/molecular transition
2. Resolving power of the instrument.
 Natural line width is influenced by:
i) Collision broadening – Due to constant random motion of the atoms / molecules, and frequent collision, small
change in the energy level occur.
ii) Doppler broadening – Random motion also results in movement of the atoms/molecules towards or away
from the detectors.
iii) Heisenberg uncertainity pricncipe:
The scientific principle stating that it is impossible to determine with perfect accuracy both the position and
momentum of a particle at any given point in time.
 INFRARED SPECTROSCOPY

Infrared Region:
IR is the portion of electromagnetic radiation that extends beyond the visible into the microwave region. It is divided
as follows:
- Near infrared (NIR) or overtone region from the visible region to 4000 cm-1.
- Mid infrared or fundamental region from 4000 to 400 cm-1. This is the segment of the infrared most often
used by organic chemists.
- Far infrared (FIR) is the low frequency region, which ranges from 400 to 10 cm-1.
-
I. PRINCIPLE OF IR SPECTROSCOPY

1. Theory of molecular vibration:

Absorbtion in IR region is due to the changes in vibrational and rotational energy levels. A vibration change is
accompanied by rotational changes and therefore IR spectra is also known as vibrational - rotational spectra.

2.Selection Rule:
➢ Gross selection rule: A molecule absorbs energy, when the energy of radiation is equal to energy difference between
the two levels involved in the transition. This energy absorbed should be able to cause a change in the dipole
moment in the molecule.
➢ Specific selection rule: ΔJ = ± 1 and ΔV= ± 1,
Where ΔJ – energy change in rotational level and ΔV – energy change in vibrational level.
3.Types of vibrations:
A molecule has got fundamental mode of vibrations. There are different types of vibrations,
1. Stretching vibrations
2. Bending vibrations.

3.1 Stretching vibrations:

There are two types of stretching vibrations
i) Symmetric stretching
ii) Assymetric stretching
i) Symmetric Stretching: In this type, the movement of the atom with respect to a particular
atom in the same direction.
ii) Assymetric Stretching: In this vibration one atom approaches the central atom while the other
departs from it.
3.2 Bending vibrations:
There are two types of bending vibrations: In-plane bending and ii) Out-of-plane bending
i) Types of in-plane bending vibrations: a) Scissoring and b) Rocking

a) Scissoring: In this type both the atoms approaches each other.

b) Rocking: In this type the movement of the atom takes place in the same direction

ii) Types of out-plane bending vibrations : a) Wagging and b) Twisting

 a) Wagging: In this type, the two atoms move up and down below the plane with respect to central
atom.
b) Twisting: In this type, one of the atom moves up the plane while the other move down with respect
to the other atom.

Fundamental modes of vibrations

for a molecule

Stretching Bending
Vibrations Vibrations

In-plane Out-of-plane
Symmetric Asymmetric bending bending
stretching stretching • Scissoring • Wagging
• Rocking • Twisting

4.Energy of a vibrational transition: (From Solution of Schrodinger wave equation)

Ev = (v +1/2) hν where ν = 0,1,2,3…

At v = 0, Ev = 0 = 1/2h ν → Zero point energy.
Frequency of vibrational transition in terms of wavenumber,
ν¯ = (ν +1/2) ωe where ωe = frequency of oscillation.

Therefore for v = 0 → v = 1,
ν¯ = (1+ ½) ωe – (1/2 ωe)
= 3/2 ωe – 1/2 ωe
= ωe (Fundamental vibration frequency)

5.For a diatomic molecule only stretching vibration takes place.

Homonuclear diatomic molecules:

Example: O2, N2, H2 → No dipole moment → No charge during stretching, therefore no IR.
Heteronuclear diatomic molecules:
Example: CO,NO,CN,HCl → Permanent dipole → Charge in this dipole during stretching produce IR
spectra.
6. The most useful vibrational frequencies are the fundamental vibrations, those that occur when molecules
absorb infrared radiation that promotes them to the first vibrationally excited state. On excitation to the second
or third excited states (or beyond), the overtone vibrational frequencies are observed. Overtones are weak.
Selection rule: i) Change in dipole moment ii) ΔJ = ± 1 ΔV= ± 1,
 For a rotational-vibrational transition:
ΔE(V,J) = ΔV + ΔJ
= ωe + 2B cm-1
7. Polyatomic molecules:

For a molecule with ‘N’ number of atoms the fundamental mode of vibration is given by 3N-5 if the

molecule is linear. Molecule is given by 3N-6 if the molecule is non-linear.

1. Example-1: Water is a triatomic non-linear molecule, therefore the number of vibration = 3N-6,
where N→no. of atoms =3
∴ the number of modes = 3(3)-6 = 3
They are Symmetric stretching, asymmetric stretching and bending mode of vibrations.All these
modes are IR active. Since this vibration causes the change in dipole moment.

2. Example – 2: CO2 is a linear molecule. Therefore the number of modes of vibration expected is given by 3N-5
where N=3, ∴ the number of modes = 3(3)-5 = 4 modes of vibrations.
They are Symmetric stretching, asymmetric stretching, bending in plane and bending out of plane. Since this
causes no change in dipole moment hence IR inactive.
 II. INSTRUMENTATION OF IR SPECTROMETER
IR spectra are obtained by detecting changes in transmittance (or absorption) intensity as a function of
frequency. Most commercial instruments separate and measure IR radiation using dispersive spectrometers or
Fourier transform spectrometers.
The components of IR Spectrophotometer are
1. Source
2. Monochromators
3. Sample holder
4. Detector
5. Recorder
Block Diagram of IR-Spectrophotometer:

Source Sample cell Monochromator Detector Recorder

1. Source:

The most commonly used sources in IR are i) Nernst Glower ii) Globar

i) Nernst Glower: It consists of rod, made up of mixture of oxides of thorium, zirconium and yttrium. These
are mounted on ceramic tables and they are connected externally by platinum wires. These are non-
conductant at room temperature and hence as to be heated before use. The main disadvantage, it is not
sturdy or steady and hence requires a stabilizer.

ii) Globar: It consists of a rod made up of silicon carbide. This is placed inside a brass tube which is cooled
by the circulation of cold water. The brass tube has got a small slit for the passage of radiation. This silicon
carbide rod is connected to the external sources by means of aluminium wires. Globar is sturdier than the
Nernst glower but it has got a low life and cannot be used about 1200°C.

iii) Nichrome

2. Monochromator:

It is necessary to select a desired frequency from a radiation source and reject radiation of other
frequencies. This can be achieved by the use of monochromators which are of two types a) Prism Monochromator
and b) Grating Monochromator.

3. Sample cell:

The sample cell cannot be made of glass or quartz as these are opaque to IR radiation. Hence the
optical systems in IR spectrophotometer are usually made up of alkali halides like sodium chloride,
sodium bromide etc. The cells are usually washed with chloroform and dried in a stream of nitrogen
before use. When the sample cells are not in use they should be kept in a desiccator.

4. Sampling Technique:
The sampling technique is very important in spectroscopy. It is depending upon the nature of the
sample. For example, if sample is a gas , it is filled in the sample cell. The sample cell is usually made
up of alkali halides of length 10 cms. It is completely sealed on one sides contains a alkali halide
window which can be closed and opened.

If the sample is liquid it should be crystal clear (neat solution) it can be filled as suc h in the sample
tube. If it is not clear it is dissolved in a suitable solvent to get a crystal clear solution. This solution
is then filled up in the alkali halide cell and then it is closed with the transparent alkali halide plates.

If the sample is a solid two different methods are adopted. i) Mull technique ii) Pressed pellet
technique.

i) Mull technique: In this technique the sample is mixed with a mineral oil nujol to form a
paste and this paste is smeared on the thin alkali halide film. It is then cov ered with an other
alkali halide film such that the sample is sandwich between two alkali halide films. It is
then kept in the path of radiation for spectral analysis.

ii) Pressed pellet technique: In this method the sample is mixed with potassium bromide and
then pressed in to thin pellets using a pressing machine. This pellet is now kept in the path
of radiation for analysis.

Detectors:

The detectors can be classified into three categories, thermal detectors (Non-selective), pyroelectric detectors and
photoconducting detectors (selective).

i) Thermal Detectors:
Thermal detectors can be used over a wide range of wavelengths and they operate at room
temperature. Their main disadvantages are slow response time and lower sensivity relative to other
types of detectors.

Thermocouple: A thermocouple consists of a pair of junctions of different metals; for example, two
pieces of bismuth fused to either end of a piece of antimony. The potential difference (voltage)
between the junctions changes according to the difference in temperature between the junctions.
Several thermocouples connected in series are called a thermopile.

Bolometer:A bolometer functions by changing resistance when heated. It is constructed of strips of

metals such as platinum or nickel or from a semiconductor.

ii) Pyroelectricdetectors
Pyroelectric detectors consists of a pyroelectric material which is an insulator with special thermal
and electric properties. Triglycine sulphate is the most common material for pyroelectric infrared
detectors.

iii) Photoconducting detectors

Photoconducting detectors are the most sensitive detectors. They rely on interactions between
photons and a semiconductor. The detector consists of a thin film of a semiconductor material such
as lead sulphide, mercury cadmium telluride or indium antimonide deposited on a nonconducting
 glass surface and sealed into an evacuated envelope to protect the semiconductor from the
atmosphere.

III. APPLICATIONS OF IR

1) The IR spectrum helps in finding out the nature of the functional group from their characteristics absorption
peaks (Qualitative analysis).

For example:

i) C=O absorbs at 1620 cm-1 to 1700 cm-1

ii) Alkanes absorbs at 2960cm-1 to 2870 cm-1

iii) Aromatic ring absorbs at 1600 cm-1 to 1500 cm-1

iv) Esters absorbs at 1770 to 1725 cm-1

v) C=C and C=N absorbs at 1690 to 1600 cm-1.

2) It helps in determining the presence of hydrogen bond and differentiating between inter and intra molecular
hydrogen bond. If a molecule has got a sharp peak at 3620 cm-1 it indicates the presence of free OH group in the
molecule. If the molecule shows a small absorption band at 3620 cm-1 and a broad band between 3500 to 3200 cm-l,
it indicates the presence of hydrogen bonding in the molecule.

To distinguish between inter and intra molecular H-bonding: The test sample is diluted progressively
using a non-polar solvent and the IR are recorded. If the intensity of the H-bonding band in the 3500-3200 cm-1 does
not change with dilution, it indicates the presence of intramolecular hydrogen bonding in the sample. If the intensity
of the H-bonding peak decreases with dilution, it indicates the presence of inter-molecular hydrogen bonding.

3) It is used to determine purity of the samples – any additional peak in IR for a known compound suggests the
presence of impurities.

4) It is used to study the isomerism of the compound. Cis form is stabilized by hydrogen bonding and absorbs at
lower frequency.

5) Progress of the reaction: The IR spectrum can be used to follow the progress of the reaction in kinetic studies. In
examination of a small portion of the reactant mixture can be used to find out whether the desired product is formed
or not.

For example: The oxidation of secondary alcohol with chromium (VI) can be study using IR. Samples are withdrawn
at regular intervals and their IR are recorded.

Initially, the IR spectrum will consist show the alcoholic peak at 3620 cm-1. As the reaction proceeds, the intensity
of this peak decreases and a new peak 1700 cm-1 due to carbonyl group grows in intensity. After the completion of
the reaction, the spectrum shows only one band at 1700 cm-1, indicating the presence of ketone. This shows that the
reaction is completed and the whole of secondary alcohol has been oxidized to a ketone.

6) Keto – Enol tautomerism:

β-Diketones and β-keto-ester are known to exist as tautomeric mixtures. Their infrared spectra will exhibit
absorptions characteristic of both keto and enol forms, i.e. in addition to the carbonyl stretching frequency, a broad
O-H stretching frequency (typical of alcohols) and a C=C stretching frequency are also observed if keto-enol
tautomerism occurs in the molecule.

7) Reaction intermediates on catalytic surface can be determined.

8) It is used to find out the shape of the molecule. The shape of the molecule whether it is linear or non-linear can be
predicted by IR studies.

9) The structure of metal carbides can be studied using IR spectrum.

10) It is also used to determine the reaction rates.

11) Extensively used in forensics – to predict time of death, to find forgery through the determination of the dyes in
the inks, etc.

************************
 UV – VISIBLE SPECTROSCOPY

I. PRINCIPLE:
1. The UV-visible spectral region starts from 1000 – 4000 Å. UV-visible spectrum arises due to the electronic
transition with in the molecule.
2. When a molecule interacts with an electromagnetic radiation the electron undergoes transition from the lower
energy level to the higher energy level, the electron is now said to be in an excited condition. This electron in
the excited condition can have different types of motion. They are the rotational motion, vibrational motion,
the translational motion and electronic transition.
3. Electronic Transitions:

When a molecule is subjected to the electromagnetic radiation the electrons present in the ground state are excited to
the higher energy level. The ground level electron is termed as bonding energy level while the exiting level is termed
as the antibonding level. Depending upon the nature of the electrons different types of transitions possible in UV
spectrum are

 → *, n→ *, n→ * and  → * Transitions

  → * Transitions

• This type of transition occur between the bonding σ and the antibonding σ* orbitals of organic
molecules
• The energy required for this type of transitions is large.
• Region for  → * transition is far or vaccum uv
• Examples – alkanes and cycloalkanes, methane (which has only C-H bonds, and can only
undergo  → * transitions) shows an absorbance maximum at 125 nm, ethane – 135 nm, cyclohexane
– 150 nm

3.2 n→ *Transitions

• Observed in molecules containing hetero atoms (N, O, S or halogens)

• This kind of transition takes place when the unshared pair of electrons on the hetero atom excites to
the antibonding orbital
• Examples: λmax values for water – 167 nm, methanol – 183 nm, methyl chloride – 173 nm, methyl
iodide – 258 nm
 3.3 n→ * Transitions

• Observed in molecules containing hetero atoms (N, O, S or halogens)

• n→ * transitions occurs between the non-bonding orbitals and antibonding * orbitals
• These transitions usually occurs in longest wavelength regions of UV and visible spectrum
• This transition results in weak absorption bands
• Examples: λmax values for C=O – 279 nm, NO2 – 275 nm

3.4  → * Transitions

• Observed in molecules containing hetero atoms (N, O, S or halogens)

• → * transitions occurs between the bonding  orbitals and antibonding * orbitals
• The absorption bands due to these transitions are found to be strong
• Example: λmax of ethylene with C=C shows strong absorption band at 165 nm

Selection rules:

1. Spin selection rule: ∆S = 0

Allowed transitions: singlet → singlet or triplet → triplet

Forbidden transitions: singlet → triplet or triplet → singlet

Changes in spin multiplicity are forbidden.

2. Laporte selection rule: there must be a change in the parity (symmetry) of the complex. Electric dipole transition
can occur only between states of opposite parity.

Laporte-allowed transitions: g → u or u → g

Laporte-forbiddentransitions: g → g or u → u

g stands for gerade –compound with a center of symmetry

u stands for ungerade –compound without a center of symmetry.

Franck Condon principle:

Franck – condon principle states that electronic transition takes place so rapidly that a vibrating molecule does not
change its inter-nuclear distance appreciably during the transition.

Absorbtion law

Theory of many molecules absorbs ultraviolet or visible light. The absorbance of a solution increases as attenuation
of the beam increases. Absorbance is directly proportional to the path length, l, and the concentration, c, of the
absorbing species. Beer's Law states that

A = εcl, where ε is a constant of proportionality, called the absorbtivity.

Different molecules absorb radiation of different wavelengths. An absorption spectrum will show a number of
absorption bands corresponding to structural groups within the molecule.

Factors affecting absorption bands:

a) Chromophores and auxochromes:

i) Chromophores: Chromophore is a multiple bonded group (C=C, C=N, C=O, N=N, etc.,). The
presence of chromophore gives rise to strong absorption of radiation.
ii) Auxochromes: An auxochrome is an auxillary group which interacts with the chromophore causing
a bathochromic shift. Typical examples are amino and substituted amino groups (NH2, NHR and NR2),
hydroxyl and alkoxy groups. These are saturated groups which increase the intensity of the colour and
shift the absorption towards a longer wavelength.

b) Bathochromic, Hypsochromic, Hyperchromic and Hypochromic shifts:

i) Bathochromic shift: Shift of the absorption maxima (λmax) from a lower wavelength region to the
higher wavelength region. Bathochromic shift occurs when an auxochrome is introduced into
chromophore,It is also termed as red shift.
ii) Hypsochromic shift: When there is a shift of absorption maxima from a higher λ region to lower λ
region, the shift is termed as hypsochromic shift or blue shift.
iii) Hyperchromic shift: Shift of the absorption band from lower intensity to a higher intensity is termed
as hyperchromic shift.
iv) Hypochromic shift: Shift of the absorption band from higher intensity to a lower intensity is termed
as hypochromic shift.

Instrumentation:

Spectrophotometr: The spectrophotometer makes use of monochromators to cut of the unwanted radiations and it
uses the modern devices like photo tube, photomultiplier tube as the detectors.

The components of UV-Visible Spectrophotometer are

i) Source
ii) Monochromators
iii) Sample holder
iv) Detector
v) Recorder
Block Diagram of UV-Visible Spectrophotometer:

Source Monochromator Sample cell Detector Recorder

Source:

Generally there are two types of radiation.

i) Thermal source ii) Discharge tube

i) Thermal source: This consists of tungsten filament lam. The filament is heated to about 3000 K. When
it starts emitting radiation which save as a source of UV spectrum. When the lamp is heated to about
 4000K. The intensity of the radiation is quite high. However, the life of the source is considerably reduced.
The source is usually heated to about 3000 K.

ii) Electric discharge tube: There are different types of electric discharge source.

a) Hydrogen discharge lamp b) Deutrium c) Xenon

In this source of long glass tube is taken and is filled with hydrogen, deuterium or xenon. It is then sealed and an
electric arc is struck between the two electrodes at very low pressure. The gas gets heated and starts glowing and
starts producing radiation which can be used as a source for uv spectrum. In most of the gases, the gas taken is
hydrogen. The intensity of the deuterium lamp is five times greater than hydrogen lamp but the cost is very high and
therefore lamps are not used.

Monochromator:

It is necessary to select a desired frequency from a radiation source and reject radiation of other
frequencies. This can be achieved by the use of monochromators which are of two types a) Prism Monochromator
and b) Grating Monochromator.

Sample cell:

The sample cell is usually made up of silica or quartz .It consists of a long tube made up of silica into
which the sample under investigation is taken in the form of the solution. If the substance or the
sample is solid, it is dissolved in a solvent to get a clear solution. The solvents generally used are
water, alcohol, ether, CCl 4 and CHCl 3 .

Detectors:

The detectors mainly used in UV-vis spectrophotometer are of three types.

i) Phototube ii) Photomultiplier tube iii) Diode array detector

Applications:

1. It is used to determine structure of the compound.

2. It is used in the determination of the atomic grouping in a given molecule. For eg: A keto group absorbs at
1600 cm-1 and between 1800-2700 cm-1. Thus any compound giving a band at this region indicates the
presence of keto group

3. Qualitative analysis: It is used to detect the presence or absence of certain groups in the organic molecules.
For eg. If an organic compound exhibits no λmax above 200 n, it cannot have a conjugated chromophore (e.g,
C=C-C=C)

4. The impurities present in the given solvent can be determined using UV-vis spectroscopy. The bands obtained
due to impurity are usually very intense.For eg: cyclohexane is an important solvent. It is usually contaminated
with benzene and therefore if a sample of cyclohexane gives two absorption bands it shows that it is
contaminated with benzene. Cyclohexane gives the band at 245 nm while benzene gives the band at 255 nm.

5. It is also used to determine the strength of hydrogen bonding.

6. It is also used to study the chemical reactions and its kinetics.

7. It is used to study the isomerism of the compound.

8. It is used to study the phenomenon of tautomerism. For e.g, acetoacetic ester exhibits keto enol tautamerism.
The spectrum of acetoacetic ester gives two absorbtion bands at 275 nm and 244 nm showing that acetoacetic
ester exists in the two forms, the keto form and the enol form. There is always equilibrium with the two forms.

9. It is used to study the different photometric titrations.

10. It is also used to study the charge-transfer complexes.