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FY Photochemistry MM

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59 views16 pages

FY Photochemistry MM

Uploaded by

shksaman15
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Photochemistry

FYBSc
Dr. Mustaqeem
Paper-2 Unit 1.2
Photochemistry is the study of
the interaction of
electromagnetic radiation with
matter resulting into a physical or
chemical change.
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.
Quantum Yield or Efficiency
In terms of Quantum efficiency :

Quantum Efficiency 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 + Cl 2 → 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 + Br → HBr + Br
.
2
Reasons of high & low quantum yield
• All photochemical reactions occur in two stages
• Primary process: reacting molecules undergo
activation by absorption of light
Cl2 + hv 2Cl*
Secondary process: activated molecules undergo
photochemical change
.
Cl + H2 HCl + H Dark reactions

H + Cl2 HCl + Cl
Chain reaction
. .
H +H +M H2 + M* Recombination
reactions (chain
Cl + Cl + M Cl2 + M* is terminated)
Reasons for High Quantum Yield:
 Primary step produces free radicals initiating a series of
chain reactions
 Formation of intermediate product acting as catalyst
 Exothermic reaction -heat may activate other molecules

Reasons for Low Quantum Yield:


 Occurrence of processes involving deactivation of excited
molecules before they form products
 The fragments may recombine

 Loss of energy by collision with non-energised molecules


Photochemical Reactions

• Combination of H2 & Cl2 :-


➢Quantum yield is 105 -106
➢Cl2 + h ν Cl◦ + Cl◦ ( Initiation )
❑ Cl◦ + H2 HCl + H◦
❑ H◦ + Cl2 HCl + Cl◦
✓Cl◦ + Cl◦ Cl2 ……. requires high energy
✓H◦ + H◦ H2 ……. requires high energy
✓H◦ + Cl◦ HCl
• If the reaction mixture is contaminated with oxygen,

• Cl◦ + O2 ClO2
• 2 H◦ + ½ O2 H2O
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:
◼ Chemiluminescence: The emission of light in
chemical reaction at ordinary temperature is
called Chemiluminescence
e.g. The light emitted by glow-worms
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.
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.
Thank
You

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