Photochemistry

Dr. Gagandeep Singh

Department of Chemistry,
Punjabi University College,
Ghudda, Bathinda.
Punjab
• Scheme:

Photophysical process
Absorption Law
Laws of Photochemistry
Photochemical reactions
Fluorescence Quenching
 Absorption & Emission

Rapid process(10-15s)
Absorption & Emission
Mechanisms of Light Absorption
Excitation:

h
X2 X2*

A bonding electron is lifted to a higher energy level

(higher orbital)
 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)
 Singlet and Triplet Excited States

Spin multiplicity 2S+1, S= ± 1/2

Fluorite CaF2, Flouresceine dye, Vapours of Sodium, Mercury, Iodine

Many dyes when dissolved in Glycerol or fused boric acid and then
cooled to rigid mass, become phosphorescent
According to Lambert-Beer law, when a beam of monochromatic
radiation passes through any solution, the intensity of the beam reduces to
some amount. Let if I0 is the intensity ofincident beam and It is the intensity of
transmitted beam, then the intensity of energy absorbed Ia is given by
Ia = I0 – It
Also the amount of light intensity absorbed by the sample is directly
proportional to the concentration and the thickness of the absorption material.
i.e.
dI/I = – acdx …..(2)
Where dI is change in intensity after travelling through the sample, dx is
the thickness of the absorption sample with concentration c and a is the
proportionality constant. Where minus sign indicated that there is decrease in
intensity. Integration Eq. 2 between I = I0 to I = I at x = b gives
In(I/I0) = 2.303 log(I/I0) = – abc …….(3)
The amount of intensity, when passing through any sample decreases
exponentially with increase in thickness of the sample and the concentration
of the medium. This phenomenon of decrease in intensity with medium and
concentration is called Lambert-Beer law.
 Beer-Lambert Law
Beer-Lambert Law: I0 = intensity of incident light
I = intensity of transmitted light

log(I0/I) = lc  = molar absoptivity coefficient in

cm2 mol-1
 = A/cb c = concentration in mol L-1
l = pathlength of absorbing
A = lc solution in cm-1

A = c (when b is 1 cm) A = absorbance = log(Io/I)

A= Log 1/T
Transmittance:
The ratio I/Io of intensity (I) of transmitted light from the solution to the
intensity of incident light (Io) i.e.

T= I/Io
 Molar absorptivities ()
Molar absoptivities are very large for strongly absorbing
chromophores ( >10,000) and very small if the absorption is
weak (= 10 to 100).
The magnitude of  reflects both the size of the chromophore
and the probability that light of a given wavelength will be
absorbed when it strikes the chromophore. A general equation
stating this relationship may be written as follows:

 = 0.87 x 1020P x a
where P is the transition probability (0 to 1)
a is the chromophore area in cm2
The transition probability depends on a number of factors
including where the transition is an “allowed” transition or a
“forbidden” transition
 1
A=bc
certain 
T=10-A =10- bc
A b s o rb a n c e , A
constant b

Transmittance, T
One analyte
0.5

Slope = b

Concentration Concentration

Transmittance decreases
Beer’s law is a relation between
exponentially as concentration
absorbance and concentration which
increases
is a straight line passes by origin at
constant pathlength, b, and at certain
wavelength, .

Beer’s law is obeyed for

monochromatic light
 Deviations from the Beer-Lambert Law

Low
c

High
The Beer-Lambert law assumes
c
that all molecules contribute to
the absorption and that no
absorbing molecule is in the
shadow of another
Absorption: Intensity

The absorption efficiency of an analyte is affected by:

The nature of the analyte
The number of available microstates
The solvent (sort of)
The absorption efficiency of an analyte generally not
affected by:
Temperature (within reason)
Concentration
This makes absorption spectroscopy one of the few
bioanalytical methods where the signal intensity is
directly proportional to the concentration
Laws of Photochemistry

1. Only light that is absorbed can produce

photochemical change (Grotthus, Draper)

2. A molecule absorbs a single quantum of light

is becoming excited (Stark, Einstein)
Grothus–Draper Law

When light falls on a cell containing a reaction mixture, some light is

absorbed and the remaining light is transmitted. Obviously, it is the
absorbed component of light that is capable of producing the reaction.
The transmitted light is ineffective chemically. Early in the 19th century,
Grothus and Draper studied a number of photochemical reactions and
enunciated a generalisation. This is known as Grothus-Draper law

It is only the absorbed light radiations that are effective in producing a

chemical reaction. However, it does not mean that the absorption of
radiation must necessarily be followed by a chemical reaction. When the
conditions are not favourable for the molecules to react, the light energy
remains unused. It may be re-emitted as heat or light.

The Grothus-Draper law is so simple and self-evident. But it is purely

qualitative in nature. It gives no idea of the relation between the
absorbed radiation and the molecules undergoing change.
Stark-Einstein Law of Photochemical Equivalence

Stark and Einstein (1905) studied the quantitative aspect of

photochemical reactions by application of Quantum theory of light. They
noted that each molecule taking part in the reaction absorbs only a
single quantum or photon of light.

The molecule that gains one photon-equivalent energy is activated and

enters into reaction.

One particle of a chemical substance can absorb only

one photon from a light beam: E = h

For one mole: E = Nh

N = Avogadro’s number (6.02 · 1023)

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)

 = wavelength

 = frequency
Chemical bond energies:
from 100 – 1000 kJ/mol

Light energies:
604 kJ/mol-1 302 151
 ULTRAVIOLET VISIBLE INFRARED

200 nm 400 nm 800 nm

So UV – and VIS region is expected to induce chemical

reactions.
Quantum Efficiency:

To relate the number of quanta absorbed with the number of

reacting molecules.

 = number of molecules undergoing the process

number of quanta absorbed
of Quantum
efficiency
Chemical reactions accompanied with light.

1.Action of light → chemical change

(light induced reactions)

2. Chemical reaction → light emission

(chemiluminescence)
Luminescence:

- Chemiluminescence:

P4 (g) + O2 (g)+H2O (g) P4 O10 + h

green

- Bioluminescence: - mushrooms
- insects
- fishes
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

h
X2 X + X (photodissociation)
(energy of the photon supplies the „dissociation heat”)
Photodissociation
Photolysis of hydrogen bromide
h
HBr H + Br (photochemical reaction)

H + HBr H2 + Br
(dark reactions)
Br + Br Br2

Overall:
h
2HBr H2 + Br2

1 photon absorbed, 2 molecules of HBr dissociated:

2
QUANTUM YIELD = 1 = 2
 Ozone formation in the atmosphere
(at about 25 km altitude)

h
O2 O+O (<240 nm)

2O2 + 2O (+M) 2O3 (+M*)

M absorbs energy released in the reaction

2
QUANTUM YIELD = =2
1
 Ozone formed in the reaction above absorbs UV
light as well:

h
O3 O2 + O (<340 nm)

O + O3 2O2

Notes:

1.Ozone shield protects the Earth surface from

high energy UV radiation (of the Sun)

2.Air pollution (freons: fully halogenated hydrocarbons;

nitrogen oxides emitted by aeroplanes etc.) may
accelerate the decomposition of ozone  ozone hole
Photosynthesis

The photosynthesis of hydrogen chloride

Overall reaction:

Cl2 + H2 2HCl [no reaction in darkness]

Mechanism:

h
Cl2 < 500 nm
2Cl Photochem. initiation

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)

Note:

Quantum yield is about 106 (explosion)

• Photosynthesis of HBr:

hv
H2 + Br2 → HBr
1  Br2 +hv→ 2 Br· chain initiation

2  Br· + H2 → H· + HBr chain propagaton

3  H· + Br2 → HBr + Br· chain propagation

4  H· + HBr → H2 + Br· chain inhibition

5  2 Br· + M → M* + Br2 Chain Termination

Quantum efficiency about 0.01 at ordinary temperature

Photosensitized reactions

Photosynthesis in plants

Overall reaction:

h; chlorophyll
6CO2 + 6H2O C6H12O6+6O2
several steps
carbohydrate
1. Chlorophyll acts as a catalyst absorbing and
transferring the photon energy for reduction of
carbon dioxide to carbohydrate

2. This reaction maintains the life on the Earth:

CO2; H2O
sunlight carbohydrate

Fossile energy
Food
(coal, oil, natural gas)
Fluorescence quenching

Any process that decreases the fluorescence intensity of a sample. A variety of

molecular interactions can result in quenching. These include excited-state
reactions, molecular rearrangements, energy transfer, ground-state complex
formation, and colli-sional quenching.
THANKS