Photochemistry

Introduction

ENERGY

Heat Electricity Electromagnetic

irradiation (light)
Vision: Triggered by a photochemical reaction
Is red in the dark?

The answer must be NO -

Since what we see as colour
must be light which is
reflected off the object.

In darkness this cannot

happen.
Photochemistry
Chemical reactions accompanied with light.

Photochemistry is the study of the interaction of

electromagnetic radiation with matter resulting into a
physical change or into a chemical reaction

1. Action of light → chemical change

(light induced reactions)

2. Chemical reaction → light emission

(chemiluminescence)
 Definitions and terms
Light: electromagnetic vibrations
spreading in quanta
(photons)

Photon: the smallest amount of light

carries energy
(wavelength) x (frequency) = speed λν = c
Distance and Size scales of the Electromagnetic Spectrum
E=hν
 Photochemical Vs Thermal reactions
S. No. Photochemical reactions Thermo-chemical reactions
1. These involve the These involve either absorption
absorption of light. or evolution of heat.
2. Take place in presence of Take place in dark or in presence
light. of light.
3. They are independent of They are dependent of
temperature. temperature.
4. Rate of reactions is Rate of reactions is not affected
dependent on the by the intensity of light.
intensity of the light
absorbed.
5. The free energy change is The free energy change is always
negative or positive. negative.
Grotthuss-Draper law:

Only the light absorbed in a molecule can produce

photochemical Change in the molecule

(1871 -1841)
Stark – Einstein law:

If a species absorbs radiation, then one particle is

excited for each quantum of radiation absorbed
 He I
h = 23.1eV
3p
3s
hν hν’
2p
2s
He I
h = 21.2 eV

1s
Scheme of photochemical reaction

h
A A* I B+C
Intermediates Stable products
In terms of Quantum efficiency :

No. of molecules reacting in a given time

Quantum Efficiency ф= ________________________________
No. of quanta's of light absorbed at same time

Experimentally,

rate of chemical reaction

ф=
quanta absorbed per second.

Stark - Einstein:

If a species absorbs radiation, then one particle is

excited for each quantum of radiation absorbed
Energy of photons (A. Einstein)

E = h = h c

h = Planck’s constant (6.6 · 10-34 Js)

C = speed of light (3 · 108 ms-1)

λ = wavelength

ν = frequency
Einstein’s Equivalency Principle
One particle of a chemical substance can absorb only
one photon from a light beam: DE = h

For one mole: DE = Nh= One Einstein

N = Avogadro’s number (6.02 · 1023)

Photons ≡ quanta

One molecule absorbs ≡ one photon

One mole of a substance one mole of quanta (or)

Containing 6.023 x 1023 ≡ 6.023 x 1023 quanta of

(Avogadro number) light (or) one Einstein

Molecules absorbs
E = h  E = hc
 = c 
   


6.610 Js  310 m s 
34

8

E=    =
 nm 109 m

21016 J
 nm
N
1 1.6 10 19 
1000

1234 eV 119627 kJ mol

 nm  nm
Numerical value of Einstein
In CGS Units
E=2.86/λ(cm) cal / mole
or
2.86X105 / λ(A0) K cal /mole

In SI units
E=0.1197/λ(m) J mol -1
or
11.97X10-5/λ(m) KJ mol-1
 Lambert’s Law

I
x
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 dI
 I or  = kI
dx dx
which on integration changes to
I
ln =  k x (or) I = I0e-kx
I0
Where I 0 = intensity of incident light.
I = intensity of transmitted light.
K = absorption co efficient.
 C
x
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
 = IC
dx
dI
(or )  = IC
dx
which on integration changes to, I=I0 e- єCx

Where, є = Molar absorption coefficient

On combining both laws, we get

log I0/I = єCx

A = log I0/I = єCx

Mathematical statement of Beer-Lambert’s law

In the above equation,

є = Molar absorption coefficient= k/2.303

A = log I0/I is the absorbance (or) Optical density (OD)
A solution shows a transmittance of 20% when taken in a
cell of 2.5cm thickness. Calculate its concentration if the
molar absorption coefficient is 12,000 dm3/mol.cm ?

%T= 20% » T = 0.20, x = 2.5cm, ε = 12,000 dm3/mol.cm

We know that, A = εCx

A  log T
C = =
x x

 log 0.20 0.699

C= =
12000  2.5 12000  2.5

= 2.33 x 10-5 mol/dm3

Limitations of Beer-Lambert’s law

The law is not valid

i) When non-monochromatic radiation is used,

ii) If temperature changes during measurements,

iii)The law is applicable only to dilute solutions,

iv)Deviation may occur, if the solution contains

impurities or dissociation or association
Classification of photochemical reaction
based on quantum yield

Three categories

•The reaction in which ф is a small integer like 1, 2…

Ex: a) Dissociation of HI & HBr, b) Combination of SO2 + Cl2 and

c) Ozonisation of O2

•The reaction in which ф <1

Ex: a) Dissociation of NH3, CH3COCH3 & NO2 and

b) Transformation of maleic acid into fumaric acid.

•The reaction in which ф is extremely high

Ex: a) Combination of CO with Cl2 and b) Combination of H2 with Cl2

The overall photochemical reaction consists of

i) Primary reaction
ii) Secondary reaction

•In the primary reaction, the quantum of light is absorbed by a molecule ‘A’
formations an excited molecule ‘A*’

A + hν →
In the secondary reaction, the excited molecules react further to give the
product of higher quantum yield.

→ B
Reasons for high quantum yield

Absorption of radiations in the first step involves

production of atoms or free radicals, which initiate a
series of chain reactions

Formation of intermediate products will act as a

catalyst

If the reactions are exothermic, the heat evolved may

activate other molecules

The active molecules may collide with other

molecules and activate them
 Decomposition of HI
primary reaction,
one HI molecule absorbs a photon and dissociated to produce
one H and one I.
HI + hν → H* + I*

secondary reaction

H* + HI → H2 + I*

I* + I* → I2

Overall reaction: 2HI + hν → H2 + I2

The overall reaction shows that the two HI are decomposed

for one photon (hν).
Thus, the quantum yield (ϕ) = 2/1=2
 Formation of HCl

Primary reaction: Cl2 + hν → 2 Cl*

Secondary reaction:
Cl* + H2 → HCl + H*

H* + Cl2 → HCl + Cl*

The Cl atom consumed in step 2 is regenerated in step 3……..

this will propagate the chain reaction. The chain reaction gets terminated
when the Cl atoms recombine at the walls of the vessel, where they lose their
excess energy.

H* + Cl* → HCl

Cl* + Cl* → Cl2

4 6
Reasons for low quantum yield

 Excited molecules may get deactivated before they form

products

 Excited molecules may lose their energy by collisions

with non-excited molecules

 Molecules may not receive sufficient energy to enable

them to react

 Recombination of dissociated fragments will give low

quantum yield.
Dimerization of anthracene to dianthracene

2C14H10 + hv → C28H20

The quantum yield = 2,

but actually it is found to be = 0.5;

the reason is the above reaction is reversible

C28H20 → 2C14H10
A chemical actinometer is a device, used to measure the amount
of radiation absorbed and rate of photochemical reaction.

Uranyl oxalate actinometer is a commonly used

It consists of 0.05 M oxalic acid and 0.01 M Uranyl sulphate in

water.

When it is exposed to radiation, Oxalic acid undergoes

decomposition to give CO2, CO and H2O.

(UO2 2+) *
2+
UO2 + h

COOH
2+) * 2+
(UO2 + UO2 + CO2 + CO + H2O
COOH
The residual concentration of oxalic acid can be found out
by titrating with standard KMnO4. The amount of oxalic acid
consumed is a measure of the intensity of radiation

Calculation of the amount of radiation absorbed:

The empty cell (or) the cell filled with solvent

is exposed to radiation and reading is noted = Total incident energy
The cell is filled with the reactants and again
The reading is noted = Residual energy
Total energy absorbed
by the reacting mixture = Total incident energy – Residual energy
Photosensitization
The foreign substance absorbs the radiation and transfers
energy to the reactants is called a photosensitizer

This process is called photosensitization.

Ex:
Atomic photosensitizers : Mercury, Cadmium, Zinc and

Molecular photosensitizers: Benzophenone, Sulphur dioxide.

Quenching

When the excited foreign substance collides with another

substance it gets converted into some other product due to
the transfer of its energy to the colliding substance.
 S1 or 1D
D + hν → 1D ISC
T1 or 3D
1D → 3D hν Collision

3D + A → D + 3A

3A S0 or D
→ Products (photosensitization)
Sensitizer (Donor)
(photosensitizer is D) S1 or 1A
If,
3D → Products (quenching) T1 or 3A
hν’
(quencher is A)

S0 or A
Dissociation of hydrogen molecule

UV light does not dissociate H2 molecule, because the

molecule is unable to absorb the radiation.

But, if a small amount of mercury vapour is added,

dissociation of hydrogen takes place. Here Hg acts as
photo sensitizer

Hg + hν → Hg*

Hg* + H2 → H2* + Hg

H2* → 2H
 Vision: Early theories of light were theories of vision

Photosynthesis: Life requires the capture, storage and release of the sun’s
energy

Wald Calvin Marcus

Nobel in Medicine Nobels in Chemistry
Mechanism of Vision Mechanism of Photosynthesis
Water + Carbon dioxide = Food (carbohydrates) + Oxygen
Photosynthesis: Chll + h *Chll (electrically excited)

6 H2O + 6 CO2 + *Chll C6H12O6 + 6 O2+ Chl , ΔG= -Ve

Sun
 Mechanism of Energy transfer
Antiparallel spin
S1  1  1
S = S1  S 2 =        = 0
 2  2
Spin multiplicity = 2S+1 = 2x0+1 = 1
S0
hν Singlet Excited state
S1 Singlet Excited state S1, S2, S3, etc.,
(or)

S0 Parallel spin
 1  1
Singlet Ground state S = S1  S 2 =        = 1
T1  2  2
Spin multiplicity = 2S+1 = 2x1+1 = 3
S0
Excited Triplet state Excited Triplet state
T1, T2, T3, etc.,
 Jablonski - diagram

ISC IC Excited
S1 Singlet state
Singlet S1
T1 Ground state
Fluorescence ISC
hν Radiationless S0
Deactivation Heat
hν’’
Phosphorescence
Excited
S0 Triplet state
T1
Fluorescence of Various sea stones
Phosphorescence
 Jablonski Diagram
Allowed singlet states

Forbidden triplet states

due to spin conversion
 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.
 Explanation of Jablonski Diagram

The first step is the transition from higher excited singlet

states to the lowest excited singlet state S1. This is called
internal conversion (IC). It is a non-radiative process and
occurs in less than 10-11 second .

Now from S1 the molecule return to ground state by any of

the following paths.

Path I :

The molecule may lose rest of the energy also in the form
of heat so that the complete path is non-radiative.
 Path II

Molecule releases energy in the form of light or uv

radiation. This is called Fluorescence

 Path III

Some energy may be lost in Tranfer from S1 to T1 in the

form of heat.
It is called intersystem crossing (ISC). This path is non-
radiative.

 Path IV

After ISC, the molecule may lose energy in the form of light
in going from the excited triplet state to the ground state.
This is called phosphorescence.
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 and iodine.

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.
E.g. ZnS, Sulfides and sulfates of Ca, Ba and Sr.
S. No. Fluorescence Phosphorescence

1. These involve singlet to singlet These involve triplet to singlet

transition. transition.
S1 S T1 S
0 0

2. This transition is allowed This transition is forbidden transition

transition
3. This transition is fast occurs in This transition is slow
10-8 sec
4. Efficiency is low Efficiency is more

5. It is less selective and sensitive It is more selective and sensitive

6 It is not observed in the solution It is observed in the solution

7 It stops as soon as the incident It continuous for some time even after
radiation is cut off the incident radiation is cut off
Luminescence
The glow produced in the body by methods other than
action of heat i.e. the production of cold light is called
Luminescence

Chemiluminecence

The emission of light in chemical reaction at ordinary

temperature is called Chemiluminescence

e.g. The light emitted by glow-worms

ABMO

BMO

Ar- Ar+

Ar
*
Ar