Photochemistry

Dr. B. R. Thorat,
Department of Chemistry,
Government of Maharashtra,
Ismail Yusuf College Jogeshwari (East),
Mumai 400060

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History
In 1817 the German physicist Theodor von Grotthus recognized that in order for light to
be effective in producing a chemical change it had to be absorbed
In 1841 the American chemist John William Draper studied the reaction between moist
hydrogen and chlorine gases. This reaction was first recognized photochemical reaction

After initiation of reaction, the rate of the reaction was proportional to the
intensity of the light absorbed

First law of photochemistry

(the Grotthus-Draper law

the amount of photochemical reaction is proportional to the quantity of light absorbed

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Quantitative
aspects

Photochemical reactions

Quantum theory by Max Planck in 1900 and its elucidation by

Albert Einstein in 1905

Ultra violet
or visible
light

Initiated by
absorbing

Wavelength range of about 800-100 nm

corresponding to energies of 36-286 kcal mole-l

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UV or visible

Photon
Ground state

Organic molecule
Formed by absorption of radiation
directly or indirectly

photochemical
reaction

Excited state

Product

The StarkEinstein law of photochemistry

Absorption of one photon causes the reaction of one molecule
However, the number of molecules that react is not necessarily equal to the number of photons absorbed.
Some of the excited molecules might undergo internal conversion, intersystem crossing,
fluorescence, or phosphorescence processes leading to unreactive states and therefore not react
chemically. A chain reaction might occur in which the reaction of one molecule can lead to the
reaction of other molecules without absorption of additional radiation.
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Photochemical reactions

StarkEinstein law of
photochemistry

Quantum yield

One mole of photons is called an

Einstein

>1
For chain
reaction

Non-chain
reaction, <1

>1
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Upon radiation with ultraviolet light of 300 nm to 350 nm wavelength, benzophenone

undergoes a reaction with 2-propanol to form benzpinacol and acetone

Absorption of electromagnetic radiation

to produce electronically excited states
1
Photochemical
reactions can be
considered to
occur in three
stages

2
Primary photochemical reactions involving
excited electronic states, S and T
3
Secondary or dark reactions whereby the products of the primary
photochemical reaction are converted to stable products
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Terms used in photochemistry

Excited states also can have unpaired electrons

triplet
states (T)

The excited states also can have all

electrons paired

The ground states of most molecules all

electrons are paired

States with paired electrons are called singlet states

(S1)

(S0)

Triplet state is normally are more stable than the corresponding singlet states
because, by Hund's rule, less inter-electronic repulsion is expected with unpaired
than paired electrons.
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Thermal and photochemical reactions

Thermal reactions: Thermochemistry is the study of the energy and heat associated with
chemical reactions. If a reaction releases energy and heat, it is called exothermic reaction.
The opposite is the endothermic reaction, when energy and heat is absorbed.
Photochemical reactions: Some reactions do not take place in the dark but take place only
in the presence of light or some other radiation. Such reactions are known as
photochemical reactions
Thermochemical reactions

Photochemical reactions

These reactions involve absorption or evolution of heat. These reactions involve absorption of light.
They can take place even in absence of light i.e. dark.

The presence of light is the primary requisite for the reaction to

take place.

Temperature has significant effect on the rate of a Temperature has very little effect on the rate of a photochemical
thermochemical reaction.

reaction. Instead, the intensity of light has a marked effect on

the rate of a photochemical reaction.

The free energy change G of a thermochemical The free energy change G of a photochemical reaction may

reaction is always negative.

not be negative.

They are accelerated by the presence of a catalyst.

Some

of

these

are

initiated

by the

presence

of a

photosensitizer. However a photosensitizer acts in a different

Bway
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than a catalyst.

Features of photochemical reactions

Do not take place in dark but take place in the presence of light by absorbing it
The reaction which initiate by higher energy was not initiated by irradiating it with
low energy radiations while reactions which are initiated by low energy radiations
are initiated by any other high energy radiations.
For example, a photon of violet light has highest frequency and hence the highest
energy. Hence a reaction which is initiated by violet light may not be initiated by
other colored radiations of visible light. On the other hand, a photon of red light
has lowest frequency and energy. Therefore a reaction that can be initiated by all
other radiations as well.
Temperature has very little effect on the rate of a photochemical reaction. Instead,
the intensity of light has marked effect on the rate of photochemical reaction
The free energy change of a photochemical reaction may not be negative.

There are many substances which do not react directly when exposed to light.
However, if another substance is added, the photochemical reaction starts called as
photo-sensitizer
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Laws of Photochemistry

Grotthus-Draper law or the first law of photochemistry: Only the light which is absorbed
by a molecule can be effective in producing photochemical changes in the molecules.

R
Ground state

R*
Excited state

Product

The probability or rate of absorption is given by the Lambert-Beer law.

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Laws of Photochemistry

Stark-Einstein law or the second law of photochemistry: One quantum of light is

absorbed per molecule of absorbing and reacting substance that disappears or The
absorption of light by a molecule is a one-quantum process for low to moderate light
intensity.
Number of activated molecules = Number of quanta of radiation absorbed
1R
Ground state

1h

1 R*
Excited state

Molecules which absorb photons become physically excited, and this must be
distinguished from becoming chemically active.

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Einstein energy
Chemical
reaction

For any chemical reaction, energy is required in two ways: (i) as

energy of activation Eact, and (ii) as enthalpy or heat of reaction H.

Energy of
activation

On close approach, the charge clouds of the two reacting partners repel
each other. The reactants must have sufficient energy to overcome this
energy barrier for fruitful interaction.

In photochemical reactions, the energy barrier is by passed due to electronic excitation and
one of the products may appear in the excited state
The bond dissociation energy per mole for most of the molecules lie between 150 kJ and 600
kJ. These energies are available from Avogadros number of photons of wavelengths lying
between 800 nm and 200 nm respectively, which correspond to the visible and near
ultraviolet regions of the electromagnetic spectrum.

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Einstein energy
An Avogadro number of photons is called an Einstein

E = E2 E1 = h
Where, h = Plancks constant and is the frequency of absorbed radiation
Wave number

Wave length

Einstein
energy

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Determination of Quantum efficiency using actinometer

Detection of the products in a photochemical

reaction

Mechanism of
photochemical
reaction

Measuring kinetics, there are more variables, since

we can study the effect of the intensity or the
wavelength of light on the rate of reaction
In the detection of intermediates (S or T) by spectra
we can use the technique of flash photolysis

The study of quantum

yields

The use of emission (fluorescence and

phosphorescence) as well as absorption spectroscopy:
the presence of as well as the energy and lifetime of
singlet and triplet excited states
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Determination of Quantum efficiency using actinometer

Product quantum
yields

The study of
quantum yields

Current

Physical
Device

Several
Ways

A primary quantum yield for a particular process

is the fraction of molecules absorbing light that
undergo that particular process

It determined by an
instrument called an
actinometer, which is
actually a standard
photochemical system
whose quantum yield is
known

Number of
quanta absorbed

Chemical device
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quantum yield of the

reference substance
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Physical actinometer
Principle: An actinometer is a chemical system or physical device which
determines the number of photons in a beam integrally or per unit time.
Devices used in the ultraviolet and visible wavelength ranges

bolometer,
thermopiles,
photodiodes

There are two basic modes of actinometric operation

static batch
mode

The photolysis reactor is filled with actinometer

gas, sealed off by a gas valve and covered with a
opaque hood to prevent exposure to sunlight.

During measurement, the actinometer

is uncovered and exposed to heat
radiation for a fixed of time.
Following this, the actinometer is
closed again and analyzed for
change in the gas composition

flowing gas
mode

The actinometer gas is constantly passed into

the reactor that is exposed to solar radiation.
In this case, the time interval is considered to
be the mean residence time of the gas in the
illuminated reactor. When gas passes through
the reactor, its composition is analyzed using
gas detector along with continuous
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Chemical actinometer

Principle: Chemical actinometry involves measuring of radiant flux via the yield from a
chemical reaction. It requires a chemical with a known quantum yield and easily analyzed
reaction product.
Potassium ferrioxalate is commonly used, as it is simple to use and sensitive over a wide
range of relevant wavelengths (254 nm to 500 nm).
Irradiation of ferrioxalate solution results in the reduction of Fe3+ to Fe2+ which is
estimated calorimetrically by using o-phenanthrolin as complexing agent.
The OD at 510 nm of the deep red color produced is compared with a standard.
The quantum yield for Fe2+ formation is nearly constant within the wavelength range and
shows negligible variation with temperature, solution composition and light intensity.

The recommended actinometric solution, for wavelength up to 400 nm contains 0.006 M

K3Fe(ox)3 in 0.1 N H2SO4. For longer wavelengths, a 0.15 M solution is more convenient.
Quantum yields vary between 1 .2 ( - 254-365 nm) to 1.1 at longer wavelengths
Other actinometers - malachite green leucocyanides, vanadium(V) iron(III) oxalate and
monochloroacetic acid.
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Photochemical reactions
A reaction which takes place by absorption of the visible and ultraviolet radiations is
called a photochemical reaction
Occurs after absorption
in 1012106 s
first-order
photochemical reaction
is about 1016 s1

intersystem crossing (ISC) in

1012104 s

Occurs in 1016
1015 s
Visible/
UV

Phosphorescence
in 106 101 s

Ground
state

As a consequence, excited triplet states are photochemically important.

Indeed, because phosphorescence decay is several orders of magnitude slower than most
typical reactions, species in excited triplet states can undergo a very large number of
collisions with other reactants before deactivation.
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Primary
Photochemical
Reaction

Photochemical
Reaction

Secondary
Photochemical
Reaction

A primary reaction proceeds by absorption of radiation. A secondary reaction is a

thermal reaction which occurs subsequent to the primary reaction
Example: The decomposition of HBr occurs as follows
Obeys laws of
photochemistry

Thermal rea.

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Low

Quantum yield

Photochemical
Reaction

Quantum yield

High

Reactions subsequent to the

Primary reaction (product of
primary reaction initiate the
reaction radical reaction, starting
molecule is one)

Deactivation of reacting molecules

(Collisions of fluorescence)
Occurrence of reverse of primary
reaction (polymer formation)

A reaction chain forms many

molecules per photon (chain
reaction, two or more starting
molecules)

Recombination of dissociated
fragments (fragments recombine to
starting molecules)

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Causes of low quantum yield

(a) Deactivation of reacting molecules: The excited molecules in the primary process
may be deactivated before they get opportunity to react. This is caused by collisions
with some inert molecules or by fluorescence.

(b) Occurrence of reverse of primary reaction: Here the primary reaction generally yields a
polymer. The product then undergoes a thermal reaction giving back the reactant
molecules.

(c) Recombination of dissociated fragments: In a primary process, the reactant molecules

may dissociate to give smaller fragments. These fragments can recombine to give back the
reactant. Thus the secondary reactions involving the fragments to form the product will not
occur.

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Hydrogen-Chlorine reaction (high quantum yield)

A mixture of hydrogen and chlorine is exposed to light of wavelength less than 4000 .
The hydrogen and chlorine react rapidly to form hydrogen chloride.
In the primary step, a molecule of chlorine absorbs a photon and dissociates into two Cl
atoms. This is followed by the secondary reactions stated below:
Initiation

Propagation
The Cl atom used in step (2) is regenerated in step (3). Thus the steps (2) and (3) constitute a
self-propagating chain reaction.
This produces two molecules of HCl in each cycle. Thus one photon of light absorbed in
step (1) forms a large number of HCl molecules by repetition of the reaction sequence (2) and
(3).
The chain reaction terminates when the Cl atoms recombine at the walls of the vessel where
they lose their excess energy.
Termination
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Cause of high quantum yield

(a) Reactions subsequent to the Primary reaction: One photon absorbed in a primary
reaction dissociates one molecule of the reactant. But the excited atoms that result may
start a subsequent secondary reaction in which a further molecule is decomposed.

Obviously, one photon of radiation has decomposed two molecules, one in the primary
reaction and one in the secondary reaction. Hence the quantum yield of the overall reaction
is 2.
(b) A reaction chain forms many molecules per photon: When there are two or more
reactants, a molecule of one of them absorbs a photon and dissociates (primary reaction). The
excited atom that is produced starts a secondary reaction chain.

It is noteworthy that A consumed in (2) is regenerated in (3).

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Fluorescence: George Gabriel Stokes named the

phenomenon fluorescence in 1852.
Radiative decay between states of same spin
multiplicity (i.e. S=0). Emission of electromagnetic
radiation, usually visible light, caused by excitation
of atoms in a material which then reemit
immediately (within about 10-8 seconds). The
initial excitation is usually caused by the
absorption of energy from incident radiation.
Because reemission occurs so quickly the
fluorescence ceases as soon as the exciting source
is removed.
E.g. Lamp: A fluorescent light bulb is coated on the
inside with a powder and contains a gas;
electricity causes the gas to emit ultraviolet
radiation, which then stimulates the tube coating
to emit light.
Applications: Mineralogy, gemology, chemical
sensors, fluorescence labeling, dyes, biological
detectors, and, most commonly, fluorescent
lamps. The most striking examples of fluorescence
occur when the absorbed radiation is in the
ultraviolet region of the spectrum, and thus
invisible and the emitted light are in the visible
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region.

Photochemical phenomenon

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Phosphorescence: Radiative decay between

states of different spin multiplicity (i.e. S
0). The emission of light from a substance
exposed to radiation and persisting as an
afterglow after the exciting radiation has
been removed. Unlike fluorescence, in
which the absorbed light is spontaneously
emitted about 10-8 seconds after excitation,
phosphorescence
requires
additional
excitation to produce radiation and may
last from about 10-3 seconds to days or
years depending on the circumstances.
In simple term phosphorescence is a
process in which energy absorbed by a
substance is released relatively slowly in
the form of light.
Phosphorescent substances have the ability
to store up light and release it gradually. If
the molecules of the substance can get
from the ground state to a metastable
state, and if the metastable state can
slowly decay back to the ground state via
photon emission, then we have
phosphorescence.

Meta
state

Meta stable state: Particular excited state of an

atom, nucleus, or other system that has a longer
lifetime than the ordinary excited states and that
generally has a shorter lifetime than the lowest,
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often stable, energy state. (shortly is energy trap)

Chemiluminescence:. It is the generation of electromagnetic radiation as light by the release of

energy from a chemical reaction. While the light can, in principle, be emitted in the ultraviolet,
visible or infrared region.
Chemiluminescent reactions can be grouped
into three types:
1. Chemical reactions using synthetic
compounds and usually involving a highly
oxidized species such as peroxide are
commonly termed chemiluminescent
reactions.
2. Light-emitting reactions arising from a living
organism, such as the firefly or jellyfish, are
commonly termed bioluminescent reactions.

3. Light-emitting reactions which take place by

the use of electrical current are designated
electrochemiluminescent reactions.
Chemiluminescence differs from fluorescence in that the electronic excited state is derived from
the product of a chemical reaction rather than the more typical way of creating electronic
excited states, namely absorption. Here, light is generated from a chemically exothermic
reaction
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Ozone Depletion

CFCs

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Thanks

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Left

Show that, at equilibrium stage Kp of gaseous phase chemical reaction is

exponentially related to G of reaction.

Centre
Show that change of A with T at constant V = change of G with T at
constant P = decrease in entropy.

Explain, partial molal quantities are intensive properties of a solution

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Right

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