PHOTOCHEMISTRY

PHOTOCHEMICAL REACTIONS AND PHOTOCHEMISTRY

Ordinary reactions occur by absorption of heat energy from outside. The

reacting molecules are energized and molecular collisions become effective.
These bring about the reaction. The reactions which are caused by heat and
in absence of light are called thermal or dark reactions.

On the other hand, some reactions proceed by absorption of light

radiations. These belong to the visible and ultraviolet regions of the
electromagnetic spectrum (200 nm to 800 nm). The reactant molecules
absorbs photons of light and get excited. These excited molecules then
proceed the reactions.

A reaction which takes place by absorption of the visible and/or

ultraviolet radiations is called a photochemical reaction.

The branch of chemistry which deals with the study of photochemical

reactions is called photochemistry.

𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 + 𝑯𝒆𝒂𝒕 = 𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝑻𝒉𝒆𝒓𝒎𝒐𝒄𝒉𝒆𝒎𝒊𝒔𝒕𝒓𝒚

𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 + 𝑳𝒊𝒈𝒉𝒕(𝑼𝑽 𝒐𝒓 𝑽𝒊𝒔𝒊𝒃𝒍𝒆) = 𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝑷𝒉𝒐𝒕𝒐𝒄𝒉𝒆𝒎𝒊𝒔𝒕𝒓𝒚

 Demonstration of a Photochemical reaction

A mixture of hydrogen and chlorine remains unchanged with lapse of time. But
when exposed to light, the reaction occurs with a loud explosion.

A bottle is filled with equimolar

amounts of hydrogen and chlorine.
It is tightly stoppered with a
handball. When the lamp is turned
on, a beam of light falls on the
mixture through the bottom of the
bottle. The reaction occurs with an
explosion. The ball is expelled with
high velocity so that it strikes the
opposite wall of the lecture theatre.
 DIFFERENCE BETWEEN PHOTOCHEMICAL AND
THERMOCHEMICAL REACTIONS
Photochemical Reactions Thermochemical Reactions
1. These involve absorption of light 1. These reactions involve absorption or
radiations. evolution of heat.
2. The presence of light is the primary 2. These reactions can take place in dark
requirement for reactions to take as well as in light.
place.
3. Temperature has a very little effect on 3. Temperature has a significant effect
the rate of photochemical reactions. on the rate of a thermochemical
reaction.
4. ΔG for photochemical spontaneous 4. ΔG for a thermochemical reaction is
reactions may be +ve or –ve. always negative.

5. Photochemical activation is highly 5. Thermochemical activation is not

selective. The absorbed photon excites selective in nature.
a particular atom or group of atoms
which become site for the reaction.
 LAWS OF PHOTOCHEMISTRY
There are two basic laws governing photochemical reactions :

(a) The Grothus-Draper law and

(b) The Stark-Einstein law of Photochemical Equivalence

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 generalization. This is known as
Grothus-Draper law and may be stated as follows :
It is only the absorbed light radiations that are effective in producing a
photochemical 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. Stark and Einstein thus
proposed a basic law of photochemistry which is named after them. The Stark-Einstein law
of photochemical equivalence may be stated as :

In a photochemical reaction, each molecule of the reacting

substance absorbs a single photon of radiation causing
the reaction and is activated to form the products.
 Stark-Einstein Law of Photochemical Equivalence

In practice, it refers to molar quantities. That is, one mole of A absorbs one
mole of photons or one Einstein of energy, E. The value of E can be calculated
by using the expression given below:

2.859
𝐸= × 105 𝑘𝑐𝑎𝑙 𝑚𝑜𝑙𝑒 −1
𝜆
 Quantum yield (or Quantum efficiency)

It has been shown that not always a photochemical reaction obeys the Einstein law. The
number of molecules reacted or decomposed is often found to be markedly different
from the number of quanta or photons of radiation absorbed in a given time.

The number of molecules reacted or formed per photon of light absorbed is termed
Quantum yield. It is denoted by φ so that

𝑵𝒐. 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒓𝒆𝒂𝒄𝒕𝒆𝒅 𝒐𝒓 𝒇𝒐𝒓𝒎𝒆𝒅

𝝓=
𝑵𝒐. 𝒐𝒇 𝒑𝒉𝒐𝒕𝒐𝒏𝒔 𝒂𝒃𝒔𝒐𝒓𝒃𝒆𝒅

1. For a reaction that obeys strictly the Einstein law, one molecule decomposes per
photon, the quantum yield φ = 1.
2. When two or more molecules are decomposed per photon, φ > 1 and the reaction
has a high quantum yield.
3. If the number of molecules decomposed is less than one per photon, the reaction
has a low quantum yield (φ < 1 ).
 PHOTOSENSITIZED REACTIONS
In many photochemical reactions the reactant molecule does not absorb the
radiation required for the reaction. Hence the reaction is not possible. In such
cases the reaction may still occur if a foreign species such as mercury vapour is
present. The mercury atom absorbs the incident radiation and subsequently
transfers its energy to the reactant molecule which is activated. Thus the reaction
occurs. A species which can both absorb and transfer radiant energy for activation
of the reactant molecule, is called a photosensitizer. The reaction so caused is
called a photosensitized reaction.
The role of mercury vapour is that of a go-between. The mercury atom absorbs the
incident radiation and is excited. The excited atom collides with a reactant
molecule (A) and transfer to it the excitation energy. This energy is enough to
activate the molecule (A). The mercury atom returns to the original unactivated
state.

𝑯𝒈 + 𝒉𝒗 → 𝑯𝒈 ∗

𝑯𝒈 ∗ + 𝑨 → 𝑨 ∗ + 𝑯𝒈
 Examples of Photosensitized reactions

(a) Reaction between H2 and O2. This reaction is photosensitized by

mercury vapour. The product is hydrogen peroxide, H2O2.

Hydrogen peroxide
may decompose to
form water, H2O.

(b) Reaction between H2 and CO. Mercury vapour is used as

photosensitizer. The product is formaldehyde, HCHO.

Some glyoxal, CHO-CHO,

is also formed by
dimerization of formyl
radicals, HCO.
 PHOTOPHYSICAL PROCESSES

If the absorbed radiation is not used to cause a chemical change, it is re-

emitted as light of longer wavelength. The three such photo-physical
processes which can occur are :
(a) Fluorescence
(b) Phosphorescence
(c) Chemiluminescence
 Fluorescence

Certain molecules (or atoms) when exposed to light radiation of short

wavelength (high frequency), emit light of longer wavelength. The
process is called fluorescence and the substance that exhibits
fluorescence is called florescent substance. Florescence stops as
soon as the incident radiation is cut off.
Examples.
1. A solution of quinine sulphate on exposure to visible light,
exhibits blue fluorescence.
2. A solution of chlorophyll in ether shows blood red fluorescence.

Explanation.
When a molecule absorbs high energy radiation, it is excited to
higher energy states. Then it emits excess energy through several
transitions to the ground state. Thus the excited molecule emits
light of longer frequency. The colour of fluorescence depends on
the wavelength of light emitted.
 Explanation of Fluorescence

Jablonski diagram of absorbance, non-radiative decay, and

fluorescence.
 Phosphorescence
When a substance absorbs radiation of high frequency and emits light even
after the incident radiation is cut off, the process is called phosphorescence.
The substance which shows phosphorescence is called phosphorescent
substance.

Phosphorescence is mainly caused by ultraviolet and visible light. It is generally

shown by solids.

Examples.
(a) Sulphates of calcium, barium and strontium exhibit phosphorescence.
(b) Fluorescein in boric acid shows phosphorescence in the blue region at 5700 Å
wavelength.

Explanation.
𝑨 + 𝒉𝒗 → 𝑨 ∗ → 𝒔𝒍𝒐𝒘 → 𝒉𝒗′
As in fluorescence, a molecule absorbs light radiation and gets excited. While
returning to the ground state, it emits light energy of longer wavelength. In doing so
the excited molecule passes from one series of electronic states to another and
gets trapped. This shows the emission of light which persists even after the
removal of light source. Thus phosphorescence could be designated as
delayed fluorescence.
Explanation of Fluorescence Phosphorescence
 Chemiluminescence
Some chemical reactions are accompanied by the emission of visible light at
ordinary temperature. The emission of light as a result of chemical action is
called chemiluminescence. The reaction is referred to as a chemiluminescent
reaction. Such a reaction is the reverse of a photochemical reaction which
proceeds by absorption of light. The light emitted in a chemiluminescent reaction
is also called ‘cold light’ because it is produced at ordinary temperature.

Examples.
1. The glow of fireflies due to the aerial oxidation of luciferin (a protein) in the
presence of enzyme luciferase.
2. The oxidation of 5-aminophthalic cyclic hydrazide (luminol) by hydrogen
peroxide in alkaline solution, producing bright green light.
 Explanation of Chemiluminescence

In a chemiluminescent reaction, the energy released in the reaction

makes the product molecule electronically excited. The excited molecule
then gives up its excess energy as visible light while reverting to ground
state.
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