MAHATMA PHULE A.S.

C COLLEGE, PANVEL

PHOTOCHEMISTRY
CLASS – S.Y. B.Sc.
Paper -1 [Physical and Analytical Chemistry]

By – Mr. Katkar R.J.

Dept. Of Chemistry
Photochemistry

Photochemistry is the study of the

interaction of electromagnetic
radiation with matter resulting into a
physical change or into a chemical
reaction .
Primary Processes
 One molecule is excited into an electronically excited
state by absorption of a photon, it can undergo a
number of different primary processes.
 Photochemical processes are those in which the
excited species dissociates, isomerizes, rearranges, or
react with another molecule.
 Photophysical processes include radiative transitions
in which the excited molecule emits light in the form of
fluorescence or phosphorescence and returns to the
ground state, and intramolecular non-radiative
transitions in which some or all of the energy of the
absorbed photon is ultimately converted to heat.
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 co efficient.
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 = Є Ic ,which on integration changes to
I=I0 e- ЄCX
Where, Є = molar absorption coefficient or molar
extinction coefficient.
Laws governing Photochemistry
 Grotthus-Draper Law:
Only the light which is absorbed by a molecule can
be effective in producing photochemical changes in
the molecule.
 Stark-Einstein’s Law ( Second Law of
Photochemistry):
It states that for each photon of light absorbed by a
chemical system, only one molecule is activated for
a photochemical reaction. The energy absorbed by
one mole of the reacting molecules is given by
E=Nhv. This energy is called one einstein.
Numerical value of Einstein
 In CGS Units
E=2.86/λ(cm) cal per mole
or
2.86X105 / λ(A0) K cal per mole

 In SI units
E=0.1197/λ(m) J mol -1

Or
11.97X10-5/λ(m) KJ mol-1
Interpretation Of Einstein’s
Law
In terms of Quantum efficiency :

Quantum Efficieny ф=
No. of molecules reacting in a given time
No.of quantas of light absorbed in the
same time

Experimentally,

Ф =rate of chemical reaction

quanta absorbed per second.
Quantum Yield
 In the photolysis of Cl2 and H2, HCl can be as high as 1
million.
Cl2 + h  2Cl
Cl + H2  HCl + H (exothermic)
H + Cl2  HCl + H
 In the photolysis of Br2 and H2, HBr is very low i.e
about 0.01
Br2 + h  2Br
Br+ H2  HBr+ H (endothermic)
H + Br2  HBr + Br
Luminescence
 The glow produced in the body by
methods other than action of heat i.e. the
production of cold light is called
Luminescence. It is of three types:
 1. Chemiluminecence:
 The emission of lighjt in chemical reaction
at ordinary temperature is called
Chemiluminescence
e.g. The light emitted by glow-worms
Fluorescence:
Certain substances when exposed to light or
certain other radiations absorb the energy and
then immediately start re-emitting the energy.
Such substances are called fluorescent
substances and the phenomenon is called
fluorescence .
e.g Organic dyes such as eosin,fluorescein etc.
vapour of sodium,mercury,iodine etc.

Phosphorescence:
There are certain substances which continue to
glow for some time even after the external
light is cut off. Thus, phosphorescence is a
slow fluorescence.
Fluorescence and phosphorescence in terms
of excitation of electrons:

Singlet Singlet excited state S1 Triplet excited state T1

ground (pair of electorns with (pair of electrons with
state So Opposite spins but each parallel spins in different
in different orbital) Orbitals)
The exicted species can return to the ground state by
losing all of its excess energy by any one of the paths
shown in jablonski diagram.
Photosensitisation
 Photosensitized reactions:
 An electronically excited molecule can transfer its
energy to a second species which then undergoes a
photochemical process even though it was not itself
directly excited.
 Mercury acting as a photosensitizer:
Hg+hv Hg*
Hg*+H2 Hg+2H

 Chlorophyll acting as a photosensitizer

CO2+H2O+hv chlorophyll 1/6(C6H12O6)+O2

 Photochemical Equilibrium

light
A B
Thermal

Rate of forward reaction α Iabs=k1Iabs

Rate of the backward reaction α[B]=k2[B]
At Equiliubrium,
Rate of forward reaction=Rate of backward
reaction
K1 Iabs=k2[B]

or

K2/k1=Iabs/[B]

or

K=I /[B]
abs

Where K=K2/k1 is the photochemical equlibrium

Ozone : O3
A gas composed of three atoms of oxygen
bluish gas that is harmful to breathe
Nearly 90% of the Earth's ozone is in the
stratosphere and is referred to as the
ozone layer

Ozone absorbs a band of ultraviolet

radiation called UVB
Ozone-Depleting Substance(s)
(ODS):

CFCs,
HCFCs,
halons,
methyl bromide,
carbon tetrachloride,
and
methyl chloroform.
Various sources
 Effects of OLD
Skin Cancer (melanoma and nonmelanoma)
-- Premature aging of the skin and other skin

problems
-- Cataracts and other eye damage
-- Immune system suppression
The Antarctic Ozone Hole

The ozone hole is

defined as the area
having less than 220
dobson units (DU) of
ozone in the overhead
column (i.e., between
the ground and space).
 Control Measures

1.Make sure that technicians working on your

car air conditioner, home air conditioner, or
refrigerator are certified by an EPA approved
program to recover the refrigerant (this is
required by law).

2.Have your car and home air conditioner units

and refrigerator checked for leaks. When
possible, repair leaky air conditioning units
before refilling them.
3.Keep your automobile well tuned and
maintained.
4. Carpool, use mass transit, walk, bicycle,
and/or reduce driving, especially on hot
summer days.
5. Be careful not to spill gasoline when filling
up your car or gasoline-powered lawn and
garden equipment. During the summer, fill
your gas tank during the cooler evening
hours.
 Ground level Ozone Formation

Secondary Pollutant
VOCs+ NOx  Ozone
In presence of sunlight
Ozone + NOX + HCs  Smog (haze)
Photochemical Smog

O3

NO2 CO

CO PAN
NO
CO, RH
HC Haze
6:00AM 12NOON 3:00 PM
Smog Sources
Sources of Volatile Organic Carbons
Sources of NOx