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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.
Thermal reactions
G may be + ve or ve
G is always ve
Photon:
Light energies:
604 kJ/mol-1
ULTRAVIOLET
200 nm
302
151
VISIBLE
400 nm
INFRARED
800 nm
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.
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
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)
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
Quantum Efficieny =
No. of molecules reacting in a given time
No. of quanta of light absorbed in the same time
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.