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PHOTOCHEMISTRY

Topics
Photochemistry Definition
Differences between Photochemical and Thermal reactions
Laws of Photochemistry
 Grotthus Draper law
 Stark-Einstein law
 Beer Lambert law

Quantum Efficiency





Classification of reactions
Causes for low and high quantum yield - Examples
Experimental Determination of Quantum yield- Actinometer method
Determination of quantum yield by kinetics approach

Problems

Photochemistry
Photochemistry is the study of the interaction of
electromagnetic radiation with matter resulting into a physical
change or into a chemical reaction.
Chemical reactions which occur by the absorption of uvvisible radiations are called photochemical reactions.

UV 200-400 nm and Visible 400-800 nm corresponds to


electronic excitations between the energy levels of molecular
orbital's of the systems.

Differences between photochemical and Thermal


reactions
Photochemical reactions

Thermal reactions

These reactions involve absorption of


light radiations

These reactions involve absorption or


evolution of heat

These reactions occur only in the


presence of light

These reactions occur both in dark as well


as in light

G may be + ve or ve

G is always ve

Temperature has a little effect on the rate


of photochemical reaction

Temperature has a significant effect on


the rate of reaction.

Definitions and terms


Light:

electromagnetic field vibration


spreading in quanta
(photons)

Photon:

the smallest amount of light


carrying energy

Energy of photons (A. Einstein)


c
E = h = h

h = Plancks constant (6.6 x10-34 Js)


c = speed of light (3 x 108 ms-1)
= wavelength
= frequency

Einsteins Equivalency Principle


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

For one mole: E = Nh


N = Avogadros number (6.02 x 1023)

Chemical bond energies:


from 100 1000 kJ/mol

Light energies:

604 kJ/mol-1
ULTRAVIOLET

200 nm

302

151
VISIBLE

400 nm

INFRARED

800 nm

So UV and VIS region is expected to induce chemical


reactions.

Laws of Photochemistry
1. Grotthus-Draper Law (Principle of Photochemical
Activation) (First Law of Photochemistry)
Only the light that is absorbed by a substance can
produce a photochemical change.

when the conditions are not favorable for the molecules


to react the absorbed radiation may be re-emitted as
heat or light.

2. Stark Einstein Law of Photochemical Equivalence


( Second law)
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.

A + hv A* Primary step
A* B
Secondary step
A + hv B Overall reaction

3.Beer-Lamberts Law
Beer Lamberts Law states that when a
monochromatic light is allowed to pass
through a solution the change (decrease) in
intensity is proportional to the concentration
of the solution and thickness through which it
passes.
A = Cx

is molar absorptivity coefficient , C is concentration, x is the thickness or path


length

INTERACTION OF LIGHT AND MATERIALS:

a) X2* X2 + M* (excess energy transferred to


the surrounding)

b) X2* X2 + h (fluorescence or phosphorescence)

c) X2* + Y chemical reaction (excess energy


supplies the activation energy of the
reaction)

Types
2. of photochemical reactions:
a) Photodissociation
b) Photosynthesis: when a larger molecule is
formed from simple ones
c) Photosensitized reactions: when an excited
molecule supplies activation energy for the
reactants

X2

X + X (photodissociation)

(energy of the photon supplies the dissociation heat)

Photodissociation
Photolysis of hydrogen bromide

HBr

H + Br (photochemical reaction)

H + HBr

H2 + Br
(dark reactions)

Br + Br

Br2

Overall:

2HBr

H2

Br2

Note:
1 photon absorbed, 2 molecules of HBr dissociated:
QUANTUM YIELD =

2
=2
1

of molecules undergoing the process


= number
number of quanta absorbed

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

Classification of Photochemical Reactions (Based on Their Quantum


Efficiencies)

According to quantum yield, photochemical reactions may be classified into


the following three categories:
1. Reactions in which is a simple integer such as 1, 2, 3 etc. For example,
the dissociation of HI and HBr, the ozonization of oxygen.
2. Reactions in which is less than 1. For example, reaction between
hydrogen and bromine
3. Reactions in which is extremely high. For example, the combination of
hydrogen and chlorine

Causes or Reasons for high quantum yield

The quantum of energy absorbed in the primary process may be more than
required to bring about the primary reaction and the excess may be passed
on to many other reactants.

In some reactions, such as the combination of H2 and Cl2 to give HCl, one
of the reactant can absorb photon and give free radicals, which can
propagate as a chain reaction.

Formation of intermediate products will act as a catalyst.


If the reactions are exothermic, the heat evolved may activate other
molecules without absorbing the additional quanta of radiation.

Causes or Reasons for Low quantum yield

Excited molecules may get deactivated before they form products


The excited molecule formed after the absorption of photon may lose
energy by collisions, fluorescence etc resulting in low quantum yield.
The excited products may recombine to form the reactants.
The primary photochemical reaction may be reversed
Molecules may not receive sufficient energy to enable them to react.

Determination of quantum yield


Measurement of number of moles - by kinetics method
Measurement of total number of Einsteins absorbed by
chemical Actinometer method

( Refer class notes/Text Book)

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