WEST BENGAL STATE UNIVERSITY

SYLLABUS FOR CHEMISTRY (HONOURS) ON PHOTOCHEMISTRY

UNDER CHOICE BASED CREDIT SYSTEM
SEM VIH

Photochemistry
(15 Lectures) Marks: 14
Lambert-Beer‟s law: Characteristics of electromagnetic radiation, Lambert-
Beer‟s law and its limitations, physical significance of absorption coefficients;
Laws of photochemistry, Stark-Einstein law of photochemical equivalence,
quantum yield, actinometry, examples of low and high quantum yields

Photochemical Processes: Potential energy curves (diatomic molecules),

Frank-Condon principle and vibrational structure of electronic spectra; Bond
dissociation and principle of determination of dissociation energy (ground
state); Decay of excited states by radiative and non-radiative paths; Pre-
dissociation; Fluorescence and phosphorescence, Jablonskii diagram

Rate of Photochemical processes: Photochemical equilibrium and the

differential rate of photochemical reactions, Photostationary state; HI
decomposition, H2-Br2 reaction, dimerisation of anthracene; photosensitised
reactions, quenching; Role of photochemical reactions in biochemical
processes, photostationary states, chemiluminescence

Books to follow:
Ø McQuarrie, D. A. & Simons, J. D. Physical Chemistry: A Molecular
Approach, Viva Press
Ø Atkins, P. W. & Paula, J. de Atkins’ Physical Chemistry, Oxford University
Press
Ø Rakshit, P.C., Physical Chemistry, Sarat Book House
Ø Laidler, K. J. Chemical Kinetics, Pearson
Ø Castellan, G. W. Physical Chemistry, Narosa

This course is taught by

Dr. Dipankar Mondal
Assistant Professor, Department of Chemistry,
BKC College, 111/2 B.T. Road, BonHoogly,
Dunlop, Kolkata-700108
 Photochemistry
The photochemistry would logically appear to be a subdivision of
Radiation chemistry. It is the science of the chemical effects of light, where
light includes the infrared and ultraviolet, as well as the visible regions of the
spectrum, i.e., the range of wavelength from about 100 nm to 10,00 nm. The
energies of quanta in this range vary from about 1 to 10 eV, or 23 to 230 kcal
per mole. These energies are comparable in order of magnitude with the
strengths of chemical bonds.
On the other hand, if a 1,000,000 eV 𝛾-ray photon or photon from x-
ray traverses a medium, thousands of molecules may become activated
along its trajectory. As we shall see, these activations often result in
ionization of the molecules, whereas in the photochemical region, ionization
would be a rare occurrence. Radiations like a, 𝛼, 𝛽, 𝛾 rays, neutrons, and
cyclotron beams, are therefore called ionizing radiations. Usually, when we
speak of Radiation chemistry we mean the science of the chemical effects
of such highly energetic, ionizing rays.

v Photochemistry
A branch of Chemistry that deals with the study of chemical reaction
which proceed in the presence of light. This branch also includes the
study of the reactions that are accompanied by the emission of
chemical energy as radiation.
+,
𝐻' + 𝐶𝑙' 2𝐻𝐶𝑙

3456
𝐶𝐻. − 𝐶𝐻 = 𝐶𝐻' + 𝐻𝐵𝑟 𝐶𝐻. − 𝐶𝐻(𝐵𝑟) − 𝐶𝐻.
AB
+,

𝐶𝐻. − 𝐶𝐻' − 𝐶𝐻' 𝐵𝑟

Example:
(i) Photosynthesis in plants
ℎ𝜈
6𝐶𝑂' + 6𝐻' 𝑂 →𝐶?𝐻@'𝑂? + 6𝑂'
𝑐ℎ𝑙
(ii) Vison
 Our retina has two different types of cells that detect and respond to light—
rods and cones. These cells that are sensitive to light are called
photoreceptors. Rods are activated when we’re in low or dim light. Cones
are stimulated in brighter environments. Cones contain photo pigments, or
color-detecting molecules. Humans typically have three types of photo
pigments—red, green and blue. Each type of cone is sensitive to different
wavelengths of visible light.

(iii) Bioluminescence in fire fly

(iv) Phototropism
Orientation of plants towards the direction of sunlight
(v) Treatment of Jaundice of Newborn babies
Phototherapy is sometimes used to treat newborn jaundice by lowering the
bilirubin levels in baby's blood. One way is to converts a substantial fraction
of the normal toxic 4Z, 15Z form of less toxic bilirubin to the 4Z, 15E.
Moreover, photo-oxidation adds oxygen to the bilirubin so it dissolves easily
in water. This makes it easier for your baby's liver to break down and
remove the bilirubin from their blood.

(vi) Biosynthesis of Vitamin D

(vii) Photochromism
The reversible transformation of molecules between two isomeric forms
induced by the absorption of light. Cis–trans isomerization is the most
common photochromic transformation.
 (viii) Polymerization or de-polymerization

v Difference between thermal and photochemical reaction

Photochemical Reaction Thermal Reaction
(i) Photo activation with radiation (i) Thermal energy gets
of sufficient large energy (200- distributed mainly amongst
800 nm) leads to electronic different translational,
excitation followed by a rotational and vibrational
reaction. excitations, very small fractions
(ii) The energy required for a lead to electronic excitations.
successful reaction, is gained (ii) The energy of activation is
by absorption of quanta from provided by molecular collision
UV/Visible region. or the collision with reaction
(iii) Many photochemical vessel wall.
reactions proceed with (iii) The thermal reactions proceed
increase (non-spontaneous) with decrease in free energy
in free energy. (spontaneous). If increase in
(iv) The rate of photochemical free energy is involved, no
reaction depends on the reaction is possible.
intensity of the radiation (iv) The rate of thermal reaction
absorbed. depends on temperature.
(v) Photochemical reaction is
more selective than thermal (v) By heating a reaction mixture,
reaction. Using a translational energies of all the
monochromatic light, only one species in the mixtures are
species in a mixture can be increased.
excited.
v Lambert’s Law
The rate of decrease in intensity of incident radiation with the thickness
of absorbing media is proportional to the intensity of the penetrating
radiation.

𝐼K 𝐼

ℓ
If We consider a thin layer of the medium of thickness dℓ and let, I be
the intensity of the radiation entering it then
𝑑𝐼
= −𝑘𝐼
𝑑ℓ
Now, if I0 is the intensity at ℓ = 0 and I is the intensity at
distance ℓ then
I ℓ
𝑑𝐼 𝐼
𝑜𝑟 = − 𝑘 𝑑ℓ 𝑜𝑟 𝑙𝑛 = −𝑘ℓ
IJ 𝐼 K 𝐼K

𝐼 = 𝐼K 𝑒 N6ℓ
𝐼
𝐴𝑙𝑡𝑒𝑛𝑎𝑡𝑖𝑣𝑒𝑙𝑦, 2.303 𝑙𝑜𝑔 = −𝑘ℓ
𝐼K
𝐼 −𝑘
𝑙𝑜𝑔 = ℓ = −0.4343𝑘ℓ
𝐼K 2.303
𝐼
log = −𝑎ℓ, ℎ𝑒𝑟𝑒 𝑎 = −0.4343𝑘
𝐼K
𝐼 = 𝐼K 10N4ℓ , 𝑎 𝑖𝑠 𝑡𝑒𝑟𝑚𝑒𝑑 𝑎𝑠 𝑒𝑥𝑡𝑖𝑛𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
v Beer’s Law
The rate of decrease in intensity of the incident radiation with the
thickness of the absorbing media is proportional to the intensity of the
penetrating radiation and the concentration of the absorbing media.
𝑑𝐼
= −𝑘 a 𝐶𝐼, 𝑘 a 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑎𝑠 𝑚𝑜𝑙𝑎𝑟 𝑎𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
𝑑ℓ
I ℓ
𝑑𝐼 𝐼
=− 𝑘 a 𝐶 𝑑ℓ 𝑜𝑟 𝑙𝑛 = −𝑘 a 𝐶ℓ
IJ 𝐼 K 𝐼K
c dℓ
𝐼 = 𝐼K 𝑒 N6
𝐼
𝐴𝑙𝑡𝑒𝑛𝑎𝑡𝑖𝑣𝑒𝑙𝑦, 2.303 𝑙𝑜𝑔 = −𝑘 a 𝐶ℓ
𝐼K
𝐼 −𝑘 a 𝐶
𝑙𝑜𝑔 = ℓ = −0.4343𝑘 a 𝐶ℓ
𝐼K 2.303
𝐼
log = −𝜖𝐶ℓ, ℎ𝑒𝑟𝑒 𝜖 = −0.4343𝑘 a
𝐼K
𝐼 = 𝐼K 10Nfdℓ , 𝜖 𝑖𝑠 𝑡𝑒𝑟𝑚𝑒𝑑 𝑎𝑠 𝑚𝑜𝑙𝑎𝑟 𝑒𝑥𝑡𝑖𝑛𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
The molar absorption coefficient depends on the frequency of the
incident radiation and is greatest where the absorption is most intense.
Its dimensions are 1/(concentration × length), and it is normally
convenient to express it in cubic decimeters per mole per centimeter
(dm3.mol−1.cm−1).
v Relation between Transmittance and absorbance:
The ratio of the transmitted intensity, I, to the incident intensity, I0, at a
given frequency is called the transmittance, T, of the sample at that
frequency:

𝐼
𝑇=
𝐼K

We can also introduce the term the absorbance, A, of the sample at a

given wavenumber as

𝐼K
𝐴 = 𝑙𝑜𝑔
𝐼
Therefore,
1
𝐴 = 𝑙𝑜𝑔 = −log 𝑇
𝑇
100
𝑜𝑟 𝐴 = 𝑙𝑜𝑔 = 2 − log 𝑇
%𝑇
v Deviation from Beer’s Law can be observed:
(i) If the light used is not monochromatic
(ii) If the concentration of the absorbing solute is greater than 0.02 (M),
in that case Beer’s law is not correct. This is due to the interaction
among the solute particles which changes the value of molar
extinction coefficient (𝜖)
(iii) Aggregation: If the solute is partially soluble in a solvent, in that case
if may form aggregation at high concentration. The absorption
spectra of the aggregation may be different from that of the
monomers.
e.g. At concentration 10 mg/ml phenol blue is appears as red
whereas at lower concentration is is blue. Depending on the chosen
wavelength for observation, the deviation from Beer’s law may be
positive or negative.
(iv) Scattering of Light: Biological samples are mostly turbid due to
presence of macromolecules or formation of large aggregates,
therefore light is scattered by the turbid solution. The optical density
(O D) due to scattering is proportional to 1 𝜆j (𝑅𝑎𝑦𝑙𝑒𝑖𝑔ℎ 𝑆𝑐𝑎𝑡𝑡𝑒𝑟𝑖𝑛𝑔)
and may be easily recognized as background absorption which mat
increase rapidly with increase in wavelength of the radiation.
(v) Fluorescence: If the optical density of the sample is high and the
absorbing species is itself is fluorescent in that case the deviation
from Beer’s law is observed because here emitted light can reach
directly to the detector.
(vi) If the optical density of the solute in the solution is measured when
it is present in equilibrium between two forms, then the
concentration of the particular solute decreases and deviation is
observed.
(vii) The factors are due to the intrinsic property of the sample. Besides,
the instrument artifacts may provide the optical density of the
sample which may be nonlinear with the concentration.

v Laws of Photochemistry
1st Law or Grotthuss-Draper Law: Only the light which is absorbed
by the reaction system can be effective in producing the chemical
change.
It is trivial that photochemical reaction is the result of absorption
of light but absorption of light does not commence photochemical
reaction all the time. Sometimes absorption of light may increase the
thermal energy of the system and absorbed radiation may also emit in
the form of fluorescence.
2nd Law or Stark-Einstein Law: For each photon of light absorbed by
a chemical system, only one molecule is activated for subsequent
reaction.
This law is concerned with primary step of activation through
absorption of one quantum of radiation by one molecule. So, there is
one to one correspondence between number of quanta and the
number of molecule, therefore, this law is also known as “Law of
photochemical equivalence”.
What is “one Einstein”?
The energy corresponds to one mole of photon or Avogadro number
of photons is called “one Einstein”.
According to Einstein, the energy of a photon with frequency 𝜈 can be
expressed as
𝜀 = ℎ𝜈; ℎ 𝑖𝑠 𝑝𝑙𝑎𝑛𝑐𝑘′𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
So, one Einstein photon of energy is
𝑐
𝐸 = 𝑁ℎ𝜈 = 𝑁ℎ
𝜆
 6.023×10'. ×6.625×10N'u ×2.298×10@K
=
𝜆
119.59729×10?
= 𝑒𝑟𝑔𝑠/𝑚𝑜𝑙𝑒
𝜆
28.583×10j
= 𝑘𝐶𝑎𝑙/𝑚𝑜𝑙𝑒
𝜆
Law of equivalence does not mean that one molecule would react
per photon absorbed.
(i) There are several molecules which are activated by absorbing
one quanta of energy and then breaks up into many fragments,
which can take part in chemical reaction.
(ii) If molecules get excited after absorbing photon and after that
they may deactivated without any reaction.
(iii) During excitation with very intense laser, e.g. Two Photon
absorption
However, the efficiency of photochemical process is often expressed
in terms of quantum Yield (𝝓). This can really establish a relation
between the number of quanta absorbed and the number of molecules
reacting. Quantum yield may vary from 0 to ~106.
𝑇ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑖𝑛 𝑡ℎ𝑒 𝑔𝑖𝑣𝑒𝑛 𝑡𝑖𝑚𝑒
𝜙=
𝑇ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑞𝑢𝑎𝑛𝑡𝑎 𝑜𝑓 𝑙𝑖𝑔ℎ𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑎𝑚𝑒 𝑡𝑖𝑚𝑒
𝑇ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑖𝑛 𝑡ℎ𝑒 𝑔𝑖𝑣𝑒𝑛 𝑡𝑖𝑚𝑒
𝜙=
𝑇ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝐸𝑖𝑛𝑠𝑡𝑒𝑖𝑛 𝑜𝑓 𝑝ℎ𝑜𝑡𝑜𝑛 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑎𝑚𝑒 𝑡𝑖𝑚𝑒
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 (𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑟 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛)
𝜙=
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
More conveniently, if we measure the rate of formation of X in
~•€
molecules per second, , then
~•
𝑑𝑁‚
𝜙= 𝑑𝑡
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑞𝑢𝑎𝑛𝑡𝑎 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑/𝑠𝑒𝑐𝑜𝑛𝑑
 The number of quanta absorbed per second is simply the absorbed
intensity, 𝐼ƒ
𝑑𝑁‚
𝜙 = 𝑑𝑡
𝐼ƒ
When quantum yield has low value?
(i) Non utilization of the excited molecules in the photochemical
reaction
(ii) Activated molecules may loss their activity through collision with
normal molecules
(iii) The decomposed fragments may recombine to form the initial
reactants
(iv) The primary photochemical reaction may be reversed
(v) Molecules may not have sufficient amount of energy to undergo a
successful reaction
Example
(a) In absence of sensitizer during photodecomposition of oxalic acid, the
quantum yield is 0.001, which is very low at radiation wavelength 265
nm to 365 nm.

When quantum yield has high value?

(i) The activated molecule may undergo chain reaction where a large
number of molecule undergo reaction.
(ii) During intermediate formation by the catalyst in a photochemical
reaction
(iii) The activated molecule may collide with normal molecules to
activate them, which can participate in subsequent reaction.
(iv) The reaction may be exothermic one, therefore heat evolved may
activate the normal molecule to react further
Example
 (a) For the combination of H2 and Cl2 to produce HCl, quantum yield value
is 105 at excitation wavelength 400 nm. This reaction follows chain
mechanism.
(b) During decomposition of HI, one photon is absorbed, which leads to
decomposition of two HI molecules. Therefore, quantum yield of this
reaction is 2.
𝐻𝐼 + ℎ𝜈 ⟶ 𝐻 . + 𝐼 .
𝐻 . + 𝐻𝐼 ⟶ 𝐻' + 𝐼 .
𝐼 . + 𝐼 . ⟶ 𝐼'
v Actinometry
A device that measures the total amount of incident radiation on sample is
called an actinometer, and the measurement method is known as
actinometry.

Two types of actinometer are commonly used.

One is Thermopile: It consists of a number of thermocouples connected in

series, with their hot junction imbedded at a blackened surface which
absorbs almost all the incident light and converts it into heat. Calibrated
lamps of known energy are available from National Bureau of Standards.
The e.m.f. developed by the Thermofile is measured with the standard lamp
and then with the source of radiation of unknown intensity. The reaction
vessel is mounted between Thermofile and the light, and the radiation
absorbed by the reacting system is measured by the difference between
filled and empty.

Instead of Thermofile, it is possible to employ relative methods of

actinometry, which is based on chemical change produced. One of the most
reproducible reaction is the decomposition of oxalic acid photosensitized by
Uranyl salts. Uranyl ion UO‡‡' absorbs radiation from 250 nm to 450 nm,
becoming an excited ion (UO‡‡ ' )*, which decomposes oxalic acid. This
reaction has quantum yield (ϕ) 0.50

𝑈𝑂'‡‡ + ℎ𝜈 ⟶ 𝑈𝑂'‡‡ ∗
 𝑈𝑂'‡‡ ∗
+ 𝐶𝑂𝑂𝐻 ' → 𝑈𝑂'‡‡ + 𝐶𝑂' + 𝐻' 𝑂 + 𝐶𝑂

The oxalic acid concentration is easily followed by titration with

permanganate. A quartz vessel filled with the uranyl oxalate mixture can be
used exactly like the thermopile, the light absorbed being calculated from the
oxalic acid decomposed and the known quantum yield.
If a molecule is excited from ground singlet state, a set of photo-physical
processes occur before it returns to the ground state. All photo-physical
process occur can be conventionally depicted with the help of Jablonski’s
diagram. In the above diagram S1, S2 represent higher singlet electronic state
and T1 represents higher triplet states with SO denoting singlet ground state.
Each of states is accompanied with the series of vibrational fine structure
levels.
When a molecule is given sufficient amount of energy then it can
absorb that energy and will very quickly excited to higher singlet state at
femtosecond timescale (~10N@Œ 𝑆𝑒𝑐). An excited molecule will release
energy with various ways.
If the excitation energy is such that the promoted molecule reaches to
the higher vibrational energy level of S1. In that case molecule tends to be
vibrationally relaxed by releasing the excess absorb energy and will come to
the lowest vibrational state of S1. This excess energy can be lost by collision
with other molecules, this phenomenon is called vibrational relaxation. The
excited state can be vibrationally relaxed very rapidly (10N@j − 10N@' 𝑆𝑒𝑐)
before the operation of any other loss process. The molecule at lowest
vibrational level in S1 can release energy to reach their original ground
electronic state by radiative or non-radiative processes. During non-radiative
transition the energy can be lost by collision and will be appeared as heat in
the system. This type of return is called internal conversion. Internal
conversion is a Radiationless transition between states of same multiplicity.
Energy can be released rapidly by emitting a radiation, this type of return is
known as radiative process, i.e. called fluorescence which occurs at the
timescale of 10N• − 10Nu 𝑆𝑒𝑐. So, fluorescence is an emission process
between two states of same spin multiplicity.

A spin forbidden transition also may happen if excited molecule transit

from S1 to T1 state. This might be accounted due to the reason that their
potential energy surface intersects with each other. At the point of
intersection of two curves, the nuclear geometries and energy are identical.
At this instant the molecule may cross without any radiation from S1 to T1
state, this process is known as intersystem crossing (ISC). So, radiationless
transition between states of different spin multiplicity is called intersystem
crossing. It is observed due to spin orbital coupling. In case of moderately
heavy atom (e.g. ZnS), the spin orbital coupling is large in that case ISC is
appreciable. Now, the molecule at T1 try to loose energy to return to the
original ground state either by non-radiative processes or by a radiative
process, latter process is called phosphorescence.
In case of phosphorescence, energy is lower than fluorescence
therefore phosphorescence has longer wavelength. The duration of
fluorescence (10N• − 10Nu 𝑆𝑒𝑐) is faster than phosphorescence (10N• −
10N@ 𝑆𝑒𝑐). In case of phosphorescence since the path followed is spin
forbidden, the rate constant is much smaller than that of fluorescence, T1
state has the lifetime of 10NŒ − 10N. 𝑆𝑒𝑐 and therefore phosphorescence
lasts longer than fluorescence.
Electronic Spectroscopy: As a first approach of electron spectroscopy we
can use Born-Oppenheimer Approximation:
𝜓••• = 𝜓‘’‘,•“”• 𝜓–”— 𝜓5˜•
𝐸•˜• = 𝐸‘’‘,•“”• + 𝐸–”— + 𝐸5˜•
The approximate orders of magnitude of these changes are
∆𝜀‘’‘ ≈ 10. ∆𝜀–”— ≈ 10? ∆𝜀5˜•
therefore, we see vibrational changes will produce coarse structure and
rotational changes a fine structure on the spectra of electronic transition. We
should also note that pure rotational spectra are shown by molecules
possessing a permanent electric dipole moment and vibrational spectra
requires a change of dipole during the motion, electronic spectra are given
by all molecules since changes in the electronic distribution in a molecule
are always accompanied by a dipole change.
An electronic transition is made up of vibrational bands, each of which
is in turn made up of rotational lines. Initially we will ignore rotational fine
structure and discuss Vibronic transitions. The intensities of the various
vibrational bands are determined by three factors: the intrinsic strength of the
electronic transition, the population of vibrational levels, and the squared
overlap integral of the two vibrational wavefunctions, called Franck-Condon
factor. Franck-Condon factor result from the application of a more general
rule called the Franck-Condon Principle. This principle has both classical and
quantum mechanical versions. Franck-Condon states that an electronic
transition takes place so rapidly that a vibrating molecules does not
change its internuclear distance appreciably during the transition. On
a potential energy diagram therefore electronic transitions occur vertically at
same internuclear separation as ground vibrational state from where it has
been excited to. The quantum mechanical version of Franck-Condon
principle is based on the fact that the intensity of the transition is proportional
to the square of the transition moment integral:
œ”•4’ ”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘,•“”•,–”— 𝜇𝜓‘’‘,•“”•,–”— 𝑑𝜏
Now, applying Born-Oppenheimer approximation, We get
œ”•4’ œ”•4’
”•”•”4’ ”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘,•“”• 𝑣–”— 𝜇𝜓‘’‘,•“”• 𝑣–”— 𝑑𝜏
The dipole moment operator can be broken into an electronic part and a
nuclear part namely,
𝜇= 𝑞” 𝑟” = 𝑞Ÿ 𝑟Ÿ + 𝑞6 𝑟6
Ÿ 6
in which the sum over the charged particles in the molecules is broken into
a sum over electrons (index j) and a sum over nuclei (index k). Then
œ”•4’ œ”•4’ ”•”•”4’ ”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘ 𝑣–”— (𝜇‘’‘ + 𝜇• ¡ )𝜓‘’‘ 𝑣–”— 𝑑𝜏
œ”•4’ ”•”•”4’ œ”•4’”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘ 𝜇‘’‘ 𝜓‘’‘,• 𝑑𝜏‘’‘ 𝑣–”— 𝑣–”— 𝑑𝜏• ¡

œ”•4’ œ”•4’ œ”•4’ ”•”•”4’

+ 𝜓‘’‘ 𝜓‘’‘ 𝑑𝜏‘’‘ 𝑣–”— 𝜇• ¡ 𝑣–”— 𝑑𝜏• ¡

The electronic wavefunctions of two different states belong to same

orthonormal state therefore they are orthogonal. Hence,
œ”•4’ ”•”•”4’ œ”•4’”•”•”4’
𝜓‘’‘,• 𝜓‘’‘,• 𝑑𝜏‘’‘ = 0, whereas, 𝑣–”— 𝑣–”— 𝑑𝜏• ¡ ≠ 0, as two
vibrational wavefunctions belong to two different excited state so they are
not orthogonal to each other. Finally, we obtain TMI as
œ”•4’ ”•”•”4’ œ”•4’”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘ 𝜇‘’‘ 𝜓‘’‘ 𝑑𝜏‘’‘ 𝑣–”— 𝑣–”— 𝑑𝜏• ¡
œ”•4’ ”•”•”4’ œ”•4’ ”•”•”4’
𝑜𝑟 𝑇𝑀𝐼 = 𝜓‘’‘ 𝜇‘’‘ 𝜓‘’‘ 𝑣–”— 𝑣–”—
in which first term is known as Re, electronic transition dipole moment and
œ”•4’
”•”•”4’
second term is vibrational overlap integral, 𝑣–”— 𝑣–”— . The intensity of
Vibronic transition is proportional of the transition moment integral, namely
œ”•4’ '
”•”•”4’
𝐼 ∝ 𝑅‘ ' 𝑣–”— 𝑣–”—
Here, Re value measures the intrinsic strength of an electronic transition,
while Franck-Condon factor determines how the intensity is distributed
among the vibrational levels.
v Franck-Condon Principle predicts the relative intensities of Vibronic
Transition

Figure 5: Two electronic potential energy curves showing the vibrational states associated
with each electronic state. (a) The minimum of the upper curve lies almost directly over
the minimum of the lower curve. (b) the minimum of the upper curve occurs at a somewhat
greater value of the internuclear separation than for the lower curve. The shaded areas
represent the harmonic-oscillator probability densities for each vibrational state. The
vertical lines represent a series of 0 → 𝜐 a vibronic transitions.
 When an electron makes a transition from one electronic state to
another, the nuclei do not move appreciably during the transition. Electronic
transitions can therefore be depicted as vertical lines in the diagram such as
figure 5. In figure 5(a) the minima of the two electronic states lie very nearly
above each other i.e. the equilibrium bond distances are same at vibrational
ground state of both ground and excited electronic state. As the relative
intensities of 0 → 𝜐 a transition is proportional to the product of vibrational
wave functions of two vibrational state thus we will obtain a distribution of
intensities like Figure 6(a) for this system.

Figure 6: The distribution of intensities of the vibronic transitions for the case shown in (a)
Figure 5(a) and (b) Figure 5(b).
Another commonly occurring case, in which the minimum of the upper
potential energy curve lies at a somewhat greater value of the internuclear
separation than for the lower curve. In that case 0 → 0 transition is not the
most intense transition. The most intense transition as shown in figure 5(b)
is the 0 → 1 transition, and the distribution of intensities for this case is like
that given in figure 6(b).
Selection Rule of Spin multiplicity: We know
œ”•4’ ”•”•”4’ œ”•4’”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘,• 𝜇‘’‘ 𝜓‘’‘,• 𝑑𝜏‘’‘,• 𝑣–”— 𝑣–”— 𝑑𝜏• ¡

The above equation can be written out more completely as follows

œ”•4’ ”•”•”4’ œ”•4’ œ”•4’”•”•”4’
𝑇𝑀𝐼 = 𝜓‘’‘ 𝜇‘’‘ 𝜓‘’‘ 𝑑𝜏‘’‘ 𝜓• 𝜓•”•”•”4’ 𝑑𝜏• 𝑣–”— 𝑣–”— 𝑑𝜏• ¡

This equation is the basis of the electronic selection rules. If any of the
integrals is zero, the transition is formally forbidden. We say, therefore, that
there are vibrational, orbital, and spin selection rules for electronic
transitions. The spin selection rules, based on above equation, states that
œ”•4’
the integral 𝜓• 𝜓•”•”•”4’ 𝑑𝜏• must be nonzero if the transition is to be
allowed. In practice, this is the easiest selection rule to apply because a
transition is spin-allowed if and only if the multiplicities of the two states
involved are identical. No change in spin multiplicity occurs during a
transition i.e. ∆𝑆 = 0. Singlet to singlet and triplet to triplet transition are
allowed but singlet to triplet or triplet to singlet are forbidden.
As an example, we will show that the triplet→singlet transition involving the
spin functions 1 𝛼(1)𝛽(2) − 𝛽(1)𝛼(2) (singlet) and 𝛼 1 𝛼 2 (triplet) is
2
forbidden,
œ”•4’ ”•”•”4’ 1
𝜓• 𝜓• 𝑑𝜏• = 𝛼 1 𝛽 2 − 𝛽 1 𝛼 2 𝛼 1 𝛼 2 𝑑𝜏‘ @,'
2 ‘ @,'
1
= 𝛼 1 𝛽 2 𝛼 1 𝛼 2 𝑑𝜏‘ @,' − 𝛽 1 𝛼 2 𝛼 1 𝛼 2 𝑑𝜏‘ @,'
2 ‘ @,' ‘ @,'
1
= 𝛼 1 𝛼 1 𝑑𝜏‘ @ 𝛽 2 𝛼 2 𝑑𝜏‘ ' − 𝛽 1 𝛼 1 𝑑𝜏‘@ 𝛼 2 𝛼 2 𝑑𝜏‘ '
2 ‘@ ‘' ‘@ ‘'
1
= 1 0 − 0 1
2
= 0; 𝑆𝑝𝑖𝑛 𝑓𝑜𝑟𝑏𝑖𝑑𝑑𝑒𝑛
Kasha’s rule:
Kasha’ Rule, states that fluorescence will always originate from the
vibrational ground state of the lowest excited singlet level, the S 1, while
phosphorescence will originate from the vibrational ground state of the
lowest excited triplet level, the T1, regardless of which initial level the
molecule is excited too.

Michael Kasha (1920 – 2013)

Azulene and some thiocompounds observed to violate Kasha’s rule. For
these molecule transition occurs directly from S2 to SO state. Because energy
gap between S2 and S1 is higher than the energy gap between S1 and SO.
For these reason fluorescence originates from S2 state competes over
internal conversion from S2 to S1.
Why fluorescence intensity decreases due to temperature rise?
With increase in temperature, the intensity of fluorescence decreases. Since
the molecule in the excited state (S1) may follow inter system crossing (ISC)
to reach the T1 state. Thus lower proportion of molecule remain in the S1
state to undergo radiative process from S1 to SO. As a result, fluorescence
intensity decreases.

Resonance fluorescence:
When the frequency of the emitted radiation due to fluorescence is identical
with that of the absorbed radiation. The phenomenon is called resonance
fluorescence.
e.g. When the Hg-vapour atoms are excited at 253.7 nm and if pressure is
lowered in that case excited molecules come back to ground state by
emitting radiation at 253.7 nm.

E-Type delayed fluorescence:

Molecules get excited from SO to S1 state after absorption of sufficient
energy. The excited molecule can cross over to the triplet state via inter
system crossing mechanism. Now, if the energy gap between S1 and T1 is
very smaller then excited molecules at T1 state can be prompted to the S1
state again which is known as reverse intersystem crossing. Then excited
molecules at S1 state come back to SO state through radiative process. This
type of fluorescence takes a longer time and called as E-type delayed
fluorescence.

P-Type delayed fluorescence:

Molecules get excited from SO to S1 state after absorption of sufficient
energy. The excited molecule can cross over to the triplet state via inter
system crossing mechanism. Now, interaction of the two molecule in the
triplet states (triple-triplet annihilation) sends one molecule to the first excited
singlet state and other molecule returns to the singlet ground state. Now the
excited molecule at first excited singlet state will return to ground singlet state
with delayed fluorescence. This type of delayed fluorescence known as P-
type delayed fluorescence.

Photosensitized reaction:
When in a mixture, a special type of molecule called donor (D) which absorb
energy from light of a particular wavelength (characteristic of donor
molecule) and becomes excited. Subsequently transform its excitation
energy to another type of molecule present in the mixture, called acceptor
(A) and then donor molecule returns to its ground state. Now, acceptor
molecule become excited and emits radiation or undergo reaction photo-
chemically. This transfer of energy from donor (D) to acceptor (A) followed
by emission of energy is known as photosensitization.

The transfer of energy from Donor to Acceptor is possible under the following
condition:
(i) The donor excited state must have sufficiently longer lifetime to be
able to transfer its excitation energy to the acceptor molecule. Since
triplet state has the longer lifetime than singlet state therefore
photosensitization is more favorable for former than latter.
(ii) The energy of the donor molecule should be higher than the
acceptor. The common sensitizes is Benzophenone. Its energy for
S1 and T1 state is 356 kJ and 291 kJ.
(iii) The multiplicity of the donor and acceptor should be same during
energy transfer

+, I§d ƒ ¨©
𝐷 𝑆¦ 𝐷 ∗ 𝑆@ 𝐷 ∗ 𝑇@ 𝐷 𝑆¦ + 𝐴∗ 𝑇@
A⎯⎯B
ƒ ( §ª )

𝐷 𝑆¦ + 𝐴∗ 𝑆@
Sensitized fluorescence:
Taking two molecules, one exhibit fluorescence and one does not under
same condition, if these two molecules are mixed and irradiated with a
particular wavelength of radiation then both exhibit fluorescent. This
phenomenon is known as sensitized fluorescence.
e.g. Hg-vapor show resonance fluorescence when irradiated with 253.7 nm
wavelength light source. But Thallium (Tl) does not exhibit fluorescence
under same condition. Now, if the mixture of Hg-vapor and Tl are irradiated
at a wavelength 253.7 both exhibit fluorescence.
+,
𝐻𝑔 + 𝑇𝑙 𝐻𝑔∗ + 𝑇𝑙 𝐻𝑔 + 𝑇𝑙 ∗

Photosensitized decomposition:
Sometimes a normal molecules absorb so much energy from a
photosensitizer molecule that it can decomposes and photosensitizer
molecule returns to their ground state. This phenomenon is known as
photosensitized decomposition.
e.g. H2 molecule do not dissociate with irradiation at 253.7 nm light. But if a
mixture of Hg-vapor and H2 molecule are irradiated with 253.7 nm light
source then Hg atom gets excited. Then ectied mercury atom transfer its
energy (112000 cal) by collision to hydrogen molecule. 103000 cal energy is
then used up by H2 molecule to decomposes to H-atom
+,
𝐻𝑔 + 𝐻' 𝐻𝑔∗ + 𝐻' 𝐻𝑔 + 2𝐻

v Quenching
Fluorescence quenching refers to any process which decreases the
fluorescence intensity of any sample or may stopped the fluorescence from
any sample. A variety of molecular interaction can result in quenching. These
include excited-state reactions, molecular rearrangement, energy transfer,
ground-state complex formation, and collisional quenching.
If the excited molecule undergo collision with another molecule the
fluorescence will be quenched., i.e. the intensity of the emitted radiation for
fluorescence may be reduced or stopped. The quenching of fluorescence is
due to transfer of energy from the excited molecule to that one with which it
collides. At low pressure, the number of molecule per unit area is small and
the excited molecule take longer time to collide with other molecule. In that
case excited molecule releases excess energy as fluorescence. But when
the pressure increases, the number of molecule per unit area increases,
therefore, the probability of collision is higher. In that case appreciable
quenching of fluorescence is observed. In case of liquid collisions are very
frequent due to presence of large number of molecule per unit area. The
quenching of fluorescence is appreciable.

We will primarily discuss two types of quenching

(i) Dynamic or collisional quenching:
The collisional encounter between fluorophore and quencher
decreases the intensity of radiation of the emitted photon for
fluorescence, this type of quenching process is known as dynamic
or collisional quenching.

(ii) Static quenching:

Quenching can occur as a result of the formation of a
nonfluorescent complex between fluorophore and quencher without
presence of any excitation light source. When this complex absorbs
light, it immediately returns to the ground state with emission of a
photon.

v The Photostationary State

Absorbed light has an interesting effect on a system in chemical equilibrium.
The absorption of light by a reactant can increase the rate of the forward
reaction without directly influencing the rate of the reverse reaction; this
disturbs the equilibrium. The concentration of products increases somewhat,
increasing the rate of the reverse reaction. In this way the rates of the forward
and reverse reaction can be brought into balance with the system This new
state in not an equilibrium state but a stationary state, called a
Photostationary state.
The dimerization of anthracene offers a convenient example, The reaction
occurs upon irradiation of a solution of anthracene by ultraviolet solution.
The plausible mechanism of the dianthracence formation is
𝐴 + ℎ𝜈 𝐴∗ 𝑅𝑎𝑡𝑒 = 𝐼4
6¬
𝐴∗ + 𝐴 𝐴'
6-
𝐴∗ 𝐴 + ℎ𝜈 a
6®
𝐴' 2𝐴
The net rate of formation of A2 is
𝑑[𝐴' ]
= 𝑘' 𝐴 𝐴∗ − 𝑘j [𝐴' ]
𝑑𝑡
In the steady state,
𝑑[𝐴∗ ]
= 𝐼4 − 𝑘' 𝐴∗ 𝐴 − 𝑘. 𝐴∗ = 0
𝑑𝑡
𝐼4
𝐴∗ =
𝑘' 𝐴 + 𝑘.

In the Photostationary state we have additional requirement that,

~[ƒ¬ ]
=0
~•

𝑜𝑟 𝑘' 𝐴 𝐴∗ − 𝑘j 𝐴' = 0
𝑘' 𝐴 𝐴∗
𝑜𝑟 𝐴' =
𝑘j
𝑘' 𝐴 𝐼4
𝑜𝑟 𝐴' =
𝑘j 𝑘' 𝐴 + 𝑘.
 1 𝐼4
𝑜𝑟 𝐴' =
𝑘j 𝑘' 𝐴 + 𝑘.
𝑘' 𝐴
1 𝐼4
𝑜𝑟 𝐴' =
𝑘j 1 + 𝑘.
𝑘' 𝐴
𝑘3
If the concentration of monomer [A] is very high, then 1 + ≈1
𝑘2 𝐴
𝐼4
𝐴' =
𝑘j
The concentration of diantharcene is independent of monomer concentration
and for the usual equilibrium A' = K[A]' .

Secondary photochemical processes: initiation of chain reactions:

Decomposition of HI: If a molecule is dissociated into fragments as a
consequence of absorbing a quantum of radiation, extensive secondary
reactions may occur. For example, if HI molecule is brought about by the
radiation of light in the range of 200-330 nm. The chain reaction is initiated
by photolysis; many reactant molecules might be consumed as a result of
absorption of a single photon. The overall quantum yield, Φ, for such
reactions, the number of reactant molecules consumed per photon
absorbed, might exceed 1. The mechanism is

𝐻𝐼 + ℎ𝜈 𝐻+𝐼 𝑅𝑎𝑡𝑒 = 𝐼4

𝐻 + 𝐻𝐼 𝐻' + 𝐼 𝑅𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑘'

𝐼+𝐼 𝐼' 𝑅𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑘.

Other possible elementary reactions either have much higher activation

energies or require three-body collisions.
The rate of disappearance of HI is

𝑑[𝐻𝐼]
− = 𝐼4 + 𝑘' 𝐻 𝐻𝐼
𝑑𝑡
The steady state requirement is
 𝑑[𝐻]
= 𝐼4 − 𝑘' 𝐻 𝐻𝐼 = 0
𝑑𝑡
𝐼4
𝑜𝑟 [𝐻] =
𝑘' 𝐻𝐼

Combining these two equation we obtain

𝑑[𝐻𝐼]
− = 2𝐼4
𝑑𝑡
By definition quantum yield
𝑑[𝐻𝐼]
−
𝜙= 𝑑𝑡 = 2
𝐼𝑎
In a variety of experimental situations, the observed value of 𝜙 is 2.

The interesting point about photochemical reaction is that the rate of the
reaction is simply the twice the absorbed intensity and is not directly
dependent on the concentration of HI.

For example, if a mixture of chlorine and hydrogen is exposed to light in the

continuous region of the absorption spectrum of chlorine (𝜆 < 480 nm) an
extremely rapid reaction to hydrogen chloride ensues.

After irradiation of photon of 480 nm, chlorine molecule reaches to the higher
energy, the maximum instability level of the molecule then it dissociates into
Cl atoms and then Cl atom participate into a chain reaction. The quantum
yield of this reaction is 104 to 106. Quantum yield of this reaction deceases if
the impurity is present in the medium. The impurity can react with H and Cl
atoms to terminate the chain reaction. Quantum yield also can decrease if
reaction occurs at the walls of vessel.

𝐶𝑙' + ℎ𝜈 2𝐶𝑙 𝑅𝑎𝑡𝑒 = 𝐼4

Efficiency of this step is one as one photon is absorbed and one molecule of
Cl2 dissociates.
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 (𝑜𝑟 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑙' )
𝜙@ =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
 6¬
𝐶𝑙 + 𝐻' 𝐻𝐶𝑙 + 𝐻
6-
𝐻 + 𝐶𝑙' 𝐻𝐶𝑙 + 𝐶𝑙
6® 1
𝐶𝑙 𝐶𝑙'
2
If we set up the steady-state expressions for [Cl] and [H] in the usual way
Then
𝑑[𝐶𝑙]
= 𝜙1 𝐼 − 𝑘2 𝐶𝑙 𝐻' + 𝑘3 𝐻 𝐶𝑙' − 𝑘4 [𝐶𝑙] = 0
𝑑𝑡 𝑎

𝜙 𝐼𝑎 + 𝑘3 𝐻 𝐶𝑙'
𝑜𝑟 [𝐶𝑙] = 1
𝑘2 𝐻' + 𝑘4
𝑑[𝐻]
= 𝑘2 𝐶𝑙 𝐻' − 𝑘3 𝐻 𝐶𝑙' = 0
𝑑𝑡
𝑘' 𝐶𝑙 𝐻2 = 𝑘. 𝐻 𝐶𝑙2
Now, we can obtain for the rate of HCI production,
𝑑[𝐻𝐶𝑙]
= 𝑘2 𝐶𝑙 𝐻' + 𝑘3 𝐻 𝐶𝑙'
𝑑𝑡
𝑑[𝐻𝐶𝑙]
𝑜𝑟 = 𝑘2 𝐶𝑙 𝐻' + 𝑘2 𝐶𝑙 𝐻'
𝑑𝑡
𝑑[𝐻𝐶𝑙]
𝑜𝑟 = 2𝑘2 𝐶𝑙 𝐻'
𝑑𝑡
𝑑[𝐻𝐶𝑙] 𝜙 𝐼𝑎 + 𝑘3 𝐻 𝐶𝑙'
𝑜𝑟 = 2𝑘2 1 𝐻'
𝑑𝑡 𝑘2 𝐻' + 𝑘4
𝑑[𝐻𝐶𝑙] 𝜙 𝐼𝑎 + 𝑘3 𝐻 𝐶𝑙'
𝑜𝑟 =2 1 𝑘
𝑑𝑡 1+ 4 𝐻
𝑘2 '

The Photochemical reaction between 𝐻' and 𝐵𝑟'

Using light of wavelength less than 511 nm, the photochemical reaction
between 𝐻' and 𝐵𝑟' can be initiated, which follows following mechanism.
𝐵𝑟' + ℎ𝜈 2𝐵𝑟; 𝐼𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛
 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 (𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑟 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛)
𝜙” =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 (𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑟 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛) = 𝜙” ×𝐼4
Where, 𝐼4 is the intensity of the light absorbed per unit volume and per unit time.
6¬
𝐵𝑟 + 𝐻' 𝐻𝐵𝑟 + 𝐻
6- 𝐶ℎ𝑎𝑖𝑛 𝑃𝑟𝑜𝑝𝑎𝑔𝑎𝑡𝑖𝑜𝑛
𝐻 + 𝐵𝑟' 𝐻𝐵𝑟 + 𝐵𝑟
6´¬
𝐻𝐵𝑟 + 𝐻 𝐵𝑟 + 𝐻' 𝐼𝑛ℎ𝑖𝑏𝑖𝑡𝑖𝑜𝑛
6´©
𝐵𝑟 + 𝐵𝑟 𝐵𝑟' 𝑇𝑒𝑟𝑚𝑖𝑛𝑎𝑡𝑖𝑜𝑛
The steady hypothesis must be applied to the two intermediates Br and H
both of which are present at very low concentrations. The steady state
equation for bromine atom is now,
𝑑[𝐵𝑟] '
= 𝜙𝑖 𝐼 − 𝑘2 𝐵𝑟 𝐻' + 𝑘3 𝐻 𝐵𝑟' + 𝑘−2 𝐻 𝐻𝐵𝑟 − 𝑘−1 𝐵𝑟
𝑑𝑡 𝑎

=0 (𝑎)
The steady state equation for H atom is
𝑑[𝐻]
= 𝑘2 𝐵𝑟 𝐻' − 𝑘3 𝐻 𝐵𝑟' − 𝑘−2 𝐻 𝐻𝐵𝑟 = 0 (𝑏)
𝑑𝑡
Now adding equation (a) and equation (b)
We have,
𝑑[𝐵𝑟] 𝑑[𝐻] '
+ = 𝜙𝑖 𝐼 − 𝑘−1 𝐵𝑟 =0
𝑑𝑡 𝑑𝑡 𝑎

𝜙 𝑖 𝐼𝑎
[𝐵𝑟] =
𝑘−1
also
𝑘2 𝐵𝑟 𝐻'
[𝐻] =
𝑘3 𝐵𝑟' + 𝑘−2 𝐻𝐵𝑟
An expression for [H] can be obtained by inserting the expression for [Br]
 𝜙 𝑖 𝐼𝑎
𝑘2 𝐻'
𝑘−1
𝐻 = (𝑐)
𝑘3 𝐵𝑟' + 𝑘−2 𝐻𝐵𝑟
Here, the rate of formation of HBr is
𝑑[𝐻𝐵𝑟]
= 𝑘2 𝐵𝑟 𝐻' + 𝑘3 𝐻 𝐵𝑟' − 𝑘−2 𝐻 𝐻𝐵𝑟 (𝑑)
𝑑𝑡
From equation (b), we know
𝑘' 𝐵𝑟 𝐻2 − 𝑘N' 𝐻 𝐻𝐵𝑟 = 𝑘. 𝐻 𝐵𝑟2
Therefore, equation (d) becomes
𝑑[𝐻𝐵𝑟]
= 2𝑘3 𝐻 𝐵𝑟'
𝑑𝑡
𝜙 𝑖 𝐼𝑎
𝑑[𝐻𝐵𝑟] 𝑘2 𝐻'
𝑘−1
𝑜𝑟 = 2𝑘3 𝐵𝑟'
𝑑𝑡 𝑘3 𝐵𝑟' + 𝑘−2 𝐻𝐵𝑟

𝜙 𝑖 𝐼𝑎
𝑑[𝐻𝐵𝑟] 𝑘2 𝐻'
𝑘−1
𝑜𝑟 = 2𝑘3 𝐵𝑟'
𝑑𝑡 𝑘3 𝐵𝑟' + 𝑘−2 𝐻𝐵𝑟

𝜙 𝑖 𝐼𝑎
𝑑[𝐻𝐵𝑟] 𝑘2 𝐻'
𝑘−1
𝑜𝑟 =2
𝑑𝑡 𝑘−2 𝐻𝐵𝑟
1+
𝑘3 𝐵𝑟'
The quantum yield of the overall reaction is
𝑑[𝐻𝐵𝑟] 𝜙𝑖
2 𝑘2 𝐻 𝑘′2 𝐻'
𝑑𝑡 𝑘−1 '
𝜙= = = ©
𝐼𝑎 𝑘 𝐻𝐵𝑟 𝐻𝐵𝑟
𝐼𝑎 1 + −2 𝐼4 1 + 𝑘′−2
¬
𝑘3 𝐵𝑟' 𝐵𝑟'
Quantum yield is inversely proportional to the square root of the intensity. As
intensity increases, a greater proportion of the bromine atoms formed are
converted to Br' instead of entering the chain; most of the additional quanta
therefore are wasted, and the process is less efficient. Because k ' is very
small, the quantum yield is less than unity at room temperature in spite of
the fact that the HBr is formed in a chain reaction. As the temperature
increases, the increase in k ' increases the quantum yield.
Rate of this reaction is rate of the consumption of H' , which is
𝑑[𝐻2 ]
𝜐“ 𝑡 = − = 𝑘' 𝐵𝑟 𝐻2 − 𝑘N' 𝐻 𝐻𝐵𝑟
𝑑𝑡
𝑑[𝐻2 ]
𝑜𝑟 𝜐“ 𝑡 = − = 𝑘. 𝐻 𝐵𝑟2
𝑑𝑡
𝜙” 𝐼4
𝑘'
𝑘N@
𝐻2
𝜐“ 𝑡 = 𝑘. 𝐵𝑟2
𝑘. 𝐵𝑟2 + 𝑘N' 𝐻𝐵𝑟
𝜙” 𝐼4
𝑘'
𝑘N@
𝐻2
𝜐“ 𝑡 =
𝑘 𝐻𝐵𝑟
1 + N'
𝑘. 𝐵𝑟2

v Luminescence:
It is generally observed that when a metal is heated to a high temperature, it
initially becomes red hot and then white. Here light is emitted by the
application of heat.
But if the emission of radiation occurs from a body by the application of
agencies other than heat that phenomenon is called luminescence. E.g.
Fluorescence, phosphorescence.
v Chemiluminescence: This is a reverse process of photo-chemical
reaction. In a photochemical reaction chemical reaction occurs after the
absorption of light, but chemiluminescence is a phenomenon in which
emission of light by a system at ordinary temperature is possible as a
result of some chemical reactions. These chemical reactions yield the
product at excited electronic state, decay of these excited state may
produce the emission of radiation at the temperature which is normally
expected. These reactions are electron transfer or oxidation reactions.
 Most chemiluminescent reactions involve singlet excited state. The
energy required for excitation is as a result of exothermic reaction.
Example: When phosphorous is oxidized in O2 or air at low low pressure
and at temperature between -10. The greenish white luminescence is
observed due to the formation of an oxide in an excited state. These
molecules when return to their ground state resulting in emission of light in
visible range.
v Bioluminescence: This is due to biochemical reaction. The intensity of the
emitted radiation is weak and the spectra observed are broad and
structureless. The intensity varies with time.
Example: The oxidation of protein luciferin in presence of enzyme luciferase
in fireflies, produces excited complex. Once it falls back down to a ground
state a photon is released.
º ¡”œ‘54•‘
𝐿𝑢𝑐𝑖𝑓𝑒𝑟𝑖𝑛 + 𝑂' + 𝐴𝑇𝑃 𝑂𝑥𝑦𝑙𝑢𝑐𝑖𝑓𝑒𝑟𝑖𝑛 + 𝐴𝐷𝑃 + 𝑃𝑃𝑖 + 𝐿𝑖𝑔ℎ𝑡