Outline

• Interaction of radiation with matter,

• Difference between thermal and photochemical processes,

• Laws of photochemistry, Grotthus - Drapper law, Stark- Einstein law,

• Jablonsiki diagram qualitative description of fluorescence,

phosphorescence, non-radiative processes (Internal conversion,
Intersystem crossing),

• Quantum yield,

• Photosensitized reactions.
 Introduction

• Definition:

Photochemistry is the branch of chemistry which is mainly concerned

with the interaction between matter & light radiations.

Or

It can also be defined as the study of the interaction of UV-Visible

radiations with matter resulting into a physical change or into a
chemical reaction.
Difference between thermal and photochemical processes
Thermal reaction/process Photochemical reaction/processes
Involve absorption or evolution of Absorption or evolution of light
heat. radiations(UV or Visible).
Can take place even in absence of light Light is necessary hence also called as
(dark reactions). light reactions.
Temperature has significant effect on Intensity of light has significant effect on
the rate of a thermochemical reaction. the rate of a photochemical reaction.
The free energy change ∆G is always The free energy change ∆G may be
negative. Spontaneous reactions positive or negative.
hence decrease in free energy.
Can be accelerated by the presence of a Can be accelerated by the presence of a
catalyst. photosensitizer. However a
photosensitizer acts in a different way
than a catalyst. e.g. peroxides.

e.g. majority of chemical reactions are e.g. Photosynthesis, Synthesis of vitamin

belonging to this class, such as D under the skin on exposure to light,
decomposition of Calcium carbonate Bioluminescence, Synthesis of ozone in
into calcium oxide and carbon dioxide earth stratosphere from photochemical
at high temperature, decomposition of reaction of oxygen, Photo-degradation,
water molecules at high temperature. Photo-alkylation, etc.
Interaction of radiation with matter
 Significance of Photochemistry to understanding
Various natural phenomenon.
1. Photosynthesis:
Synthesis of glucose by the plants.
2. Synthesis of Ozone:
In the earth stratosphere from photochemical reaction of oxygen.
3. Synthesis of Vitamin D:
Natural synthesis of vitamin D in sunlight below the skin.
4. Phototherapy:
Treatment of jaundice in new born babies.
5. Phototropism:
Phototropism means the orientation of the growth of a plant towards the
direction of light. Plant in a sunlight shows more growth compare to the plant
in the shadow.
6. Photoperiodism:
Physiological processes such as flowering in the plant is affected by length of
exposure to sunlight. e.g. blooming in Sunflower
7. Photodynamic:
Treatment of diseases with the help of photosensitive drugs
8. Bioluminescence:
Glowing of Fire flies
 Laws of Photochemistry

Photochemistry branch is governed by following important laws:

1. Grotthus-Draper Law
2. Stark-Einstein’s Law
 Laws of Photochemistry

Grotthus-Draper Law/ Law of Photochemical activation/

First law of Photochemistry :
Only the light which is absorbed by a molecule can be effective in
producing photochemical changes in the molecule.
Reflected or transmitted light does not produce any chemical change.
Calculation of absorbed light,
Iabsorbed = Io – It
Where, Iabsorbed = Intersity of absorbed light
Io=Intensity of initial radiations
It=Intensity of transmitted radiations
 Laws of Photochemistry
Stark-Einstein’s Law/ Law of photochemical equivalence/ 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.
Or
One quantum of radiations activate one molecule for a photochemical reaction.
Energy absorbed by a molecule is equal to Planck's equations,
Therefore, Energy = E = hν= hc/λ
Where, E=Energy associated with a photon,
h= Planck's Constant= 6.626×10-34 J.S or 6.626×10-27erg.S
ν=Frequancy c=Speed of the radiations λ =Wavelength
For 1 mole, Energy = E = Nhν= Nhc/λ= 1 Einstein
Where, N=Avagadro’s number= 6.023×1023
 Laws of Photochemistry
Stark-Einstein’s Law:
Energy = E = hν= hc/λ
Where, E=Energy associated with a photon,
h= Planck's Constant= 6.626×10-34 J.S or 6.626×10-27erg.S
ν=Frequancy c=Speed of the radiations λ =Wavelength
For 1 mole, Energy = E = Nhν= Nhc/λ= 1 Einstein
Where, N=Avagadro’s number= 6.023×1023
E= 6.023×1023 X 6.626×10-34 ν
E=3.985x10-10 ν
E= 3.985 x 10-10 X 3 x 108 / λ Jmol-1
E=11.97 x 10-2 / λ Jmol-1 = 1 Einstein
The energy possessed by one mole of substance or the energy absorbed by one
mole of reacting molecule is called one Einstein.
Problem 1 :
1. Calculate energy of radiation with wavelength 1000 A0.
Solution:
According to Planck's equation,
E=hν
= Nhc ÷ λ
Given, N= Avogadro's number= 6.023×1023
h= Pancks Constant= 6.626×10-34 J.S or 6.626×10-27erg.S
C=Speed of radiations= 3×108 m/s or 3×1010 cm/s
λ= 1000 A0 =1000×10-10 m= 1000×10-8 cm
Therefore,
E = 6.023×1023 × 6.626×10-27 × 3×1010 ÷ 1000×10-8
E = 11.96×1012 erg/mole or 11.96×105 Joule/mole
Problem 2 :
1. If the value of an Einstein is 72 kcal, Calculate the wavelength of the light.
Solution:
According to Planck’s equation,
E=hν
= Nhc ÷λ
Given, N= Avogadro's number= 6.023×1023
h= Pancks Constant= 6.626×10-34 J.S
C=Speed of radiations= 3×108 m/s
E= 72 kcal = 72 x 4.184 x 103 = 301.24 x 103 J
Therefore,
λ = 6.023×1023 × 6.626×10-34 × 3×108 ÷ 301.24 x 103
λ = 0.3974 x 10-6 = 3974 x 10-10 m =3974 A0
Problem 3:
Calculate the value of the Einstein of energy for radiation of wavelength 4000 A 0.
Solution:
Energy = E = hν = Nhc/λ = 1 Einstein
h= Planck's Constant= 6.626×10-34 J.S
c= 3 x 108 m/s
λ= 4000 A0 = 4000 x 10-10 m = 4 x 10-7 m
Therefore, Einstein = 6.023×1023 X 6.626×10-34 X 3 x 108 / 4 x 10-7
Einstein=11.96 x 10-2 / 4 x 10-7 Jmol-1 = 2.99 X 105 J/mole
= 0.7146 x 105 Cal/mole
= 71.46 Kcal/mole
 Interaction of radiation with matter

• When light radiations are allowed to fall on matter, some of the

radiations are absorbed, some get reflected, some get transmitted and
some get scattered.

• In photochemistry, we study the absorption and emission of light by

matter. It consists of the study of various Photophysical Processes and
Photochemical Processes (reactions).
 Interaction of radiation with matter

• Photophysical Processes:

e.g. Fluorescence, Phosphorescence, IC, ISC.

• Photochemical Processes (reactions):

 Electronic Excitation

UV and Visible light has a sufficiently high energy therefore, it can produce
change in electron energy level i.e. called electronic excitation.
 Electronic Excitation

• According to MOT in molecules electrons are filled in bonding & non

bonding orbitals.
• The electronic transition occur from HOMO (Highest Occupied Molecular
Orbitals)to LUMO (Lowest Unoccupied molecular orbitals).
 Electronic excitations

A triplet state is more stable than the

p* An t i b o n d i n g singlet state. Because in triplet state, electrons

p Bo n d i n g are unpaired - lesser inter electronic repulsion

E Gr o u n d Si n g l e t Tr i p l e t take place, while in singlet state electrons are

St a t e St a t e St a t e
S0 S1 T1
paired, causing inter electronic repulsion and
is unstable.

Calculation of spin multiplicity of electrons= 2S+1, Where S= Electron Spin

For Singlet state= 2x0+1=1
Since S=0 For Singlet state because electron spin is paired
For Triplet State= 2x1+1=3
Since S=1 For Triplet state because electron spin unpaired
 Selection Rule

• Selection Rule:
1. Spin selection rule: Δ S = 0 allowed
2. Laporte selection rule:
• Spin selection Rule: Transition without change in multiplicities
are allowed transitions while transitions with change in
multiplicities are not allowed
Chemical bond energies: 100 – 1000 kJ/mol

Light energies: 150- 600 kJ/mole

Therefore UV and visible radiations are capable to produce chemical

changes within the molecule.

600 kJ/mol 300 150

ULTRAVIOLET VISIBLE INFRARED

200 nm 400 nm 800 nm

 Jablonski Diagram

1 0 - 1 1 Se c. Su
I . C.
S2

1 0 - 0 8 Se c. S1 I . S. C.
T1 1 0 - 0 3 -- 1 Se c.
R. D.
l i ght
R. D. l i ght
F
P
1 0- 0 9 -- 1 0- 0 6 Se c. 1 0- 0 5 -- 1 0 - 0 3 Se c.

S0

F= Fluorescence
P= Phosphorescence
ISC= Intersystem crossing
IC = Internal conversion
RD = Radiationless decay.
•When a molecule absorbs a photon of energy, electronic transition occurs
(S1 or S2 or Sn).

•A molecule in S1 state undergo one of the following four energy decay processes to
the ground state.
Fluorescence:
• Emission of a photon due to de excitation from singlet excited state to a

singlet ground state is called fluorescence.

•Fluorescence, decays rapidly after the excitation source is removed.

•Lifetime of the fluorescence is only 10–5 to 10–8 s

•E.g. Gemstones
Phosphorescence:
•Emission of photons due to de excitation from triplet excited state to

singlet ground state is called phosphorescence.

•phosphorescence may continue for some time after removing the

excitation source.

•Lifetime for phosphorescence ranges from 10–4 to 104 s.

•E.g. Stickers, Toys etc.

 Difference between Fluorescence and Phosphorescence

Fluorescence Phosphorescence
Emission of a photon by an excited Emission of photons by an excited
electron during de excitation from a electron during de excitation from a
singlet excited state to a singlet ground triplet excited state to a singlet ground
state is called fluorescence. state is called phosphorescence.

Fluorescence, decays rapidly after the phosphorescence may continue for some
excitation source is removed. time after removing the excitation source.

Lifetime for phosphorescence is large

Lifetime of the fluorescence is very compare to fluorescence.

small
E.g. Gemstones, jelly fishes etc. E.g. Stickers, Toys, bulbs etc.
 Non-radiative processes
(Internal conversion, Intersystem crossing)

Internal Conversion (IC):

During internal conversion spin multiplicities of a state remains same.
Intersystem crossing (ISC):
The molecule may undergo spin inversion to the triplet state (spin
unpaired) by a process a radiation less process.
 Quantum Yield/Efficiency

To compare the number of quantum of energy absorbed with the number of

reacting molecule, a term called quantum efficiency or quantum yield (ɸ)has
been introduced.
Definition:
It is the ratio of number of molecule reacted and number of photon absorbed at
same time.

Number of molecules reacted in a given time

therefore, ɸ = -------------------------------------------------------------------
Number of photons absorbed in same time
 Quantum Yield/Efficiency

•If a reaction obeys the Stark-Einstein law, one molecule is decomposed per
photon, then the quantum yield ϕ = 1.

• When two or more molecules are decomposed per photon, the quantum yield
ϕ > 1 and the reaction has a high quantum yield.

• When the number of molecules decomposed is less than one per photon, the
quantum yield ϕ < 1 and the reaction has a low quantum yield.

If the Stark-Einstein law is strictly followed then the quantum yield (ϕ) is unity.
Problem:
1) 1 x 10-5 moles of product were formed on absorption of 6.0 x 107 erg at 3600 Å.
Calculate quantum efficiency.
Ans.- Number of molecules reacted
Quantum efficiency (ɸ) =------------------------------------------------------
Number of quanta absorbed
Number of molecules reacted = 1 x 10-5 x 6.023 x 1023
= 6.023 x 1018 molecule
Energy of one quantum= hν = hc /λ = 6.623 x 10-27 x 3 x 1010 / 3600 x 10-8
= 5.0 x 10-12
Total energy absorbed = 6.0 x 107 erg (Given)
Total quantum absorbed= 6.0 x 107 erg / 5.0 x 10-12 = 1.2 x 1019
Quantum efficiency (ɸ)= 6.023 x 1018 / 1.2 x 1019 = 0.5

Quantum efficiency (ɸ)= 0.5

Problem:
2) A certain reaction absorbed 3 x 1018 quanta of light per second. On irradiation for 20
minutes 0.003 mole of reactant is found to be reacted. Calculate quantum yield for
the reaction.
Ans.- Number of molecules reacted
Quantum yield (ɸ) =------------------------------------------------------
Number of quanta absorbed
Number of molecules reacted = 0.003 x 6.023 x 10 23
= 1.8 x 1021 molecule
Number of quanta absorbed= 3 x 1018 x 20 x 60
= 3.6 x 1021
Quantum yield (ɸ)= 1.8 x 1021 / 3.6 x 1021 = 0.5
Quantum yield (ɸ)= 0.5
Problem:
3) When substance was exposed to light 0.0025 mole of it react in 20 minute. Calculate
quantum yield if substance absorbed 2 x 1018 photon of light per second in the
same time.
Ans.- Number of molecules reacted
Quantum yield (ɸ) =------------------------------------------------------
Number of quanta absorbed
Number of molecules reacted = 0.0025 x 6.023 x 10 23
= 1.5 x 1021 molecule
Number of quanta absorbed= 2 x 1018 x 20 x 60
= 2.4 x 1021
Quantum yield (ɸ)= 1.5 x 1021 / 2.4 x 1021 = 0.625
Quantum yield (ɸ)= 0.625
Problem:
4) A certain reaction absorbed 3 x 1016 quanta of light per second. On irradiation for 20
minutes 0.002 mole of reactant is found to be reacted. Calculate quantum yield for
the reaction. (Ans.- 0.669)
 Chemiluminescence
•Luminescence is spontaneous emission of light by a substance not resulting
from heat; it is thus a form of cold body radiation. It can be caused by
chemical reactions, electrical energy, subatomic motions or stress on a crystal.
•It is the reverse of a photochemical reaction.
•Photo chemical reaction results from the absorption of light while
chemiluminescence results due to emission of light from a chemical reaction.
A→ B* →B + hv
Examples: White phosphorus glows in air with faint greenish colour due
to its oxidation. Phosphorus oxidizes to phosphorus trioxide
(P2O3 exists as dimerP4O6) oxidises to phosphorus pentoxide
(P2O5 exists as dimer P4O10)
4P + 3O2 → P4O6* →P4O6 + hv
P4O6*+2O2 → P4O10* → P4O10 + hv
 Bioluminescence

• If the luminescence is observed in a biological system, then it is called as

bioluminescence e.g. the light emitted by glow-worms, some species of
mushroom and fishes shows bioluminescence.
e.g. Luciferin(a type of Protein in insect) in the presence of enzyme luciferase
and Mg2+ undergo oxidation to Oxyluciferin and CO2 . This Oxyluciferin gives
light and shows bioluminescence in fireflies.
 Photosensitized reactions

•Photosensitization is the process of excitation of a molecule by energy transfer

from an excited molecule.
•In this process, a donor molecule (D) absorbs a quantum light and forms an
excited molecule (D*).
•The excited donor molecule then transfers its excitation energy to an acceptor
molecule (A) in the ground state in order to excite it.
•This can be explained using the following reaction sequence:
Light absorption: D + hv D*
Sensitization: D* + A A* + D
•The donor molecule is called the sensitizer. The excited acceptor molecule A*
could take part either in photochemical reactions or in photo physical processes.
Some peroxides are used as a photosensitizer in many photochemical reactions.
Example:
A well-known example of photosensitized reaction is photosynthesis.
In photosynthesis, Chlorophyll and other plant pigments act as
photosensitizer in the synthesis of starch from carbon dioxide and water.
A simplified reaction sequence is as follows:
Chlorophyll + hv → Chlorophyll*
6CO2 + 6H2O + Chlorophyll * → C6H12O6 + 6 O2 + Chlorophyll
Thank You…