PHOTOCHEMISTAY

227

in free energy i.e. AG is always of radiation energy

UNIT-IV negative. may be
converted into free chemical
energy of products ie AG may
PHOTOCHEMISTRY A Intermolecular collisions result
be positive or negative.
4. A single atom or molecule can
in the excitation of all the be promoted to excited state
molecules to almost the same independent of the other
extent.
4.1.INTRODUCTION species present in the reaction
system. So, photochemical
Photochemistry is the study of chemical reactions
the exposure of light radiations.
The electromagnetic resulting
radiatio
fron
ns 5. To increase the average energy
activation is highly selective.
5. Molecules on absorption of
the UV-visible regions
photochemical
(2000
reaction.
- 8000 A wave length) are mainliyn of all molecules, significantly
high temperature is required.
radiation are strongly excited
used in and reaction can be carried out
The absorbed photon may cause chemical changes called easily at low temperature.
photochemical reactions or may result in processes which do not 6. These reactions can take place 6. These reactions generally take
involve a chemical change such as flourescence and by ionic as well as free radical place by free radical mechanism.
phosphorescence. But chemiluminscence is a phenomenon in which mechanism.
light is emitted as a result of chemical reaction. 7. These reactions are accelerated 7. These reactions may be
The energy provided by the UV-visible region of electromagnetic by the presence of a catalyst. accelerated by the presence of
radiation is sufficient to cause an electronic excitation in the molecule an additional substance called
and there by makes it more reactive which may result in a chemical photosensitizer.
reaction. Then with the help of absorption of radiations, many
reactions of different types (eg., : synthesis, decomposition, 4.2. LAWWS OF PHOTOCHEMISTRY
polymerisation, isomeric change, oxidation and reduction) can be 4.2.1. Grothus-Draper's Law
carried out. The comparison of thermal and photochemical reactions (1839) formulated
are given in Table 4.1. Christian von Grothus (1818) and John Drapper"only the light that
states that
Table 4.1. Comparison of Thermal and the first law of photochemistry which
produce a photochemical change in
Photochemical Reactions is absorbed by a molecule can
Thermal Reactions the molecule."
Photochemical Reactions activity to the fact that each
1. Energy of
activation is 1. Energy of activation is gained This law relates photochemical certain wavelength of light, and
provided by the collisions of chemical substance absorbs only There fore, the presence of light
by the absorption radiation.
molecules. which is unique to that substance.a photochemical reaction but the
induce
2. Rate of alone is not sufficient to wavelength to be absorbed by the reactant
reaction depends on 2. Rate of reaction independent Iight must be of a correct
temperature. of temperature and depends species.
Equivalent
3. Thermal intensity of radiation. Stark-Einstein's Law of Photochemical
reaction 4.2.2. the second
accompanied by the decrease
is 3. Free energy of photochemical Albert Einstein put forward discrete
some
as Johannes Stark (1908) and absorbed in
reaction may increase
photochemistry based the idea that light is
law of
226
 PHYSICAL CHEMISTRY-IV(Sem.-VI) PHOTOCHEMISTRy
228 that 229
photons. The law states tonly one eachsmall layer is
thicknessproportion
by
called to
of layer." the intensity of light incident
energy by each
packets of of light is absorbedalso
or one photonreaction." molecule uponit and the
quantum of light This law known as the
undergoing a photochemical Suppose a beam of light with intensity I, is
law of photochemical equivalence. ofthickness dx and dl is the incident by a layer
intensity light absorbed, then
of
absorbed light, its energy as given
If vis the frequency of the - dl = aldx
by the Planck's relation is ...(3)
AE= hv where a is a constant called absorption coefficient. Integration of
.(1)
of the substance is the above equation gives
Hence, energy absorbed per mol I=he-ax
AE = NA V ..(2) ...(4)
where lo is the intensity of incident light and I is the intensity of
conventionally known as one Einstein of energy.
and is light after absorption.
Solved Problem 1. Calculate the energy per mole of light
nm.
having wavelengths of (a) 85 nm and (b) 300 4.2.4. Beer's Law
Solution : According to Beer's law the absorption coefficient of the medium
through which light travels in proportional to concentration or
(6023 x 10 mol)(6626 x 10* Js)(3 x 10° ms-) ac c or a = &'c
E - Nghcl) = (85 x 10m) ...(5)
= ]·407 x 10 J mol-! where e' is a constant known as molar absorption coefficient. Eq.4
then becomes,
=1:407 x 10 kJ mol-!
I=het'cx ...(6)
when 2=300 nm
or = ['cx ...(7)
E =
(6023 ×10 mol)(626 x104 Js)(3 x 10° ms-l) I
(300 x 10m)
=3-986 x 10 kJ mol-!
or
log 2:303
CX ...(8)
Solved Problem 2. Calculate the value of Einstein of energy
of radiation of 4000 The quantity is known as molar extinction coefficient and
wavelength. 2:303
Solution.
IS expressed as [. The above equation becomes
E=
286x105
k cal moll =&CX ...(9)
log
the solution.
286x105 The quantity [cx is termed as optical density of
4000
-k cal mol =71:5 kcal mol-l Eq.9 is called Beer-Lambert's law.
4.2.3. Lambert's Law 4.2.5, Application of the Beer - Lambert's Law
substance
This law states that "when a beam of Beer-Lambert's law is applied in the estimation of a a solutions
passes through a homogeneous absorbing monochromatic light ua solution by comparing its light
absorbance with that of
medium the light absorbed
 PHYSICAL CHEMISTRY-IV (Sem.-V) PHOTOCHEMISTAY
230

of known concentration. Spectrophotometers and

colourimeters ar Or 0144=x103 x0| 231
used for the estimation.
concentration of.
Optical density = 0-144, c= 10 M
A series of dilute solutions of known 0-144 =Ex 10 x 0-1
and their absorbance (A) measured or
substance are prepared
spectrophotometer or colourimeter. Aplot of absorbance (A) versus using E= 1:44 x 10
concentration (C) gives a straight line (Fig. 4.1). Absorbanco Solved Problem 4. A
m motl
cm-!
measurement of the substance of unknown concentration is made solution of 005 M monoch romatic radiation is incident
under similar conditionsof the standards. The unknown concentration substance. TThe concentration of an
is then obtained from the graph by extrapolation. intensity radiation
value after
of is reduced to absorbing
ofthe initial
solution. Calculate the passing
one-fourth
through 10 em length of the
substance.
molar extinction coefficient of the
Absorbance
(A) Solution : According to Beer-Lambert's Law
log =¬CX
100
But = 0-25 = 25%, i.e.,
I 25
Unknown concentration 100
log 25
=E x 0-05 mol dm x 10 cm
Concentration (c)
[ =1-204 dm mor! cm-l
Fig. 4.1. Plot of absorbance vs concentration.
Solved Problem 5, A 0-01 M solution of a substance
Limitations of Beer-Lambert's Law absorbs 10% of an incident monochromatic light in a path of
(1) The Beer-Lambert's Law is not obeyed if the radiation used 1cm length. What would be the concentration of its solution
is not monochromatic. if it is to absorb 90% of the same radiation in the same path
(2)The law governs the absorption behaviour of dilute solutions length?
only. At higher concentrations, the relationship between A andC Solution : According to Beer-Lambert's Law
is no longer as linear.
= &CX
(3) The molecular state of the solute does not change with change log
in concentration. There are two cases.
Solved Problem 3. The optical density of a 10-3 M solution Case I.
of oxalic acid in acell of 0-2 cm long is 0-144. Calculate the = 100 - 10 = 90%
extinction coefficient. Mere Io =100% and I
= 0-01 mol
100 ... (a) where c
Solution : We know log LI = &cx log 90 =8C1*
10%
Optical density = 0-144, c = 10-5 M 100% and I=100 90 =
Case II. Here Lh =
 PHYSICAL CHEMISTRY-IV (Sem.-Vi)
PHOTOCHEMISTRY
232
100
..(b) log z = 18168 233
log 10
log (100/90) %of absorbed light = antilog
100 -
(1-8168) =65-58
Eq. (a) + Eq. (b) = log (100/10) C2 65-58
0-01 mol L-! =34-42
log 100- log 90
or
log 100- log 10 . Fraction of light absorbed= 34-42
100 =0:3442
2-0000-1-9542 0-0l mol L-!
or
2-0000-1-0000 C
a3. PHOTOPHYSICAL PROCESS
0-01 mol L Generally atoms or molecules go to excited state by
or C2
ahsorption of suitable radiation. If the absorbed radiation is not the
0-0458 cause chemical reaction, it will be
a used
= 2-2183 mol L-l
re-emitted as light of longer
wAvelength. This process is called as photophysical process.
4.3.1. Types of photophysical process
Solved Problem 6, An aqueous solution of an organic dye
absorbs 10% of the incident light. What fraction of the incident Photophysicalprocess is of twotypes: (i) Flourescence and (i)
light willthe same solution absorb ifa cellwhich is four times Phosphorescene.
longer than the first? 1, Fluorescence
When a molecule or atom absorbs radiation of higher frequency
Solution : (shorter wavelength), it gets excited. Then the excited atom or
log =ECX
molecule re-emits the radiation of the same frequency or lower
Case I. Here I, = 100%, I= 100 - 10 = 90%; x = x1 frequency within short time (about 10- sec.) This process is called
fluorescence, stops as soon as the incident radiation is cut off. The
100 substance which exhibits fluorescence is called fluorescent
log 90 =ECX1 . (a) substance.
Case II. Here Ih = 100%, I =2%, x = 4x Examples : CaF,, uranium, petroleum, organic dyes like eosin,
100
fluorescein chlorophyll, quinine sulphate solution, vapours of sodium,
log = ec(4x) .. (6) iodine, mercury, etc.
Types of Fluorescence
log (100/90) excited atom emits
Eq. (a) : Eqn. (b) (a) Resonance a fluorescence : If the
log (100/ z) 4 tne radiation of the same frequency, the process is known as
example, when mercury vapour at low
.:. 4 [log 100 log 90] = log Tesonance fluorescence. For
wavelength 253·7 nm, it gets
100- log z Pressure is exposed to radiation of its ground state, it emits
or 4 [2-0000 - 1-9542] =
2-0000- log z CXCited. Subsequently. when it returns to absorbed.
Tadiation of the same frequency, which itsmolecule is excited, due
0-1832 = 2-0000 - log z (0)Sensitized Fluorescence : If the
energy from the foreign
to the transfer of part of excitation
the process is
the radiation of lower frequency,
substance, it emits
 MOroCHEMISTAY
PHYSICAL CHEMISTAY-IV (Sem,-VI
emitted photon (light) has6. The 235
234 The
example, if the mercury vapour lower energy than the absorbed loweremitted
energy photon
%
known as sensitized fluorescence. Forthalium, lead or zinc, which do photonand emission 0ccurs at than the(light) has
absorbedat
is mixed with the vapours of silver, then exposed to the radiation. longer wavelength than the photon and emission occurs
a
not absorb radiation at 253-7 nm andmercury a longer
apart of the excitation energy from
is transferred and gets
to its ground state.
jncidentlight.
flu wavelength
orescence. than
excited to higher energy state. When it returns 2In
fluorescent materials,
immediate flash gives7.or after Phosphorescent
it emits radiation of lower frequency. an'an
glow'on excitation. appears to glow in materials
the dark'
2. Phosphorescence Examples of. Fluorescence :
because of slow emission of
frequency, the light over time.
When a substance absorbs radiation of higher Gemstones fluoresce, including
for some time even after the Examples of
Glow of clockPhosphorescence
emission of radiation is continuous :
BYpsum, talc, jelly fish,
incident light is cut off. This process is called phosphorescence (or) dial or
delayed fluorescence. The substance which shows phosphorescence
chlorophyll extract, vita nins etc bulbs after switchingtoysofforthein
is called phosphorescent substance.
light in the room. The glow
remains for some minutes
Examples : Zinc sulphide, alkaline-earth sulphides (e.g. CaS, even hours in a dark room.
or
BaS and SrS).
The comparison between fluorescenc and phosphorescence is Phosphorescent
sign board
materials in
given in Table 4.2. illuminate during
night.
Table 4.2. The comparison between Fluorescence and Phosphorescence
Aschematic representation of fluorescence and phosphorescence
Fluorescence Phosphorescence
emissions are given in Fig. 4.2.
1. It is the absorption of energy by 1. It is the absorption of energy by
atoms or molecules followed by atoms or molecules followed by Fluorescence Intersystem crossing
immediate emission of light or delayed emission of E
electromagnetic radiation. electromagnetic radiation. 3A
2. The emission of radiation or 2 The emission of radiation
light suddenly stops on removal remains for some time even after
of source of excitation. the removal of source of
excitation. phosphorescence
3. In fluorescence, the excited atom 3. In phosphorescence, the excited hy-E
hy
has comparatively short life time atom has comparatively long life
before its transition to low time before its transition to low
energy state. energy state.
4. The time period or interval 4. The time period or interval
between the absorption and between the absorption and
emission of energy is very short. emission of energy is emissions.
comparatively long. Fig. 4.2. Fluorescence and phosphorescence
5. Absorption process ocurs over'5.
short time interval and involves Phosphorescence involves the 4.3.2. Jablonski Diagram
the transition from ground state transition from the single ground
energy diagram, arranged
A Jablonski diagram is basically an levels can be quantitatively
to singlet excited state and do energy state to excited triplet
not change the direction of the state and involving a change of
spin state. with on a vertical axis. The energy
energybut schematically.
spin.
dengted, diagrams use energy levels
most of these columns. Every column
The rest of the diagram is arranged into
 PHOTOCHEMISTRY
PHYSICAL CHEMISTRY-IV (Sem.-Vi) 237
236
usually represents a specificspin multiplicity for a particular species, electrons may be either (a) parallel or (b)
However, some diagrams divide energy levels within the same spin (a) parallel (1T), then S = S + S) anti-parallel.
=
Within each column, .. 28 +
| = 3, i.e.,
spin multiplicity is 3. The(1/2) + (1/2) = 1,
multiplicity into different columns. particular molecule
lines represent eigen states for that
horizont4.3).al
(FFig. triplet(T) excited state. molecule is in the
() anti-parallel (), then S= s + s,
singlet level system triplet level system .: 2S -1=
+ 1, i.e., spin
= (1/2) - (1/2) = 0,
multiplicity is 1. The molecule is in the
singlet (S) excited state.
400
S3 Vibrational relaxation 10-12s
Since the electron can jump from the ground state to
any of
Wavelength,nm Internal conversion 10-12g the higher electronic states depending upon the energy of the
S00
photon
ahsorbed. We get a series of (a) singlet excited states i.e. S1,
Kaug ST,
So. etc., (first singlet excited state, second singlet excited state, third
600
S2 singlet excited state, etc.) and (b) triplet excitd states i.e., T,, T,,
Tn
T.. etc. (first triplet excited state, second triplet excited state, etc.).
Intersystem crossing 10s
S
Generally singlet excited state has higher energy than the
700 çorresponding triplet excited state. Thus, the energy sequence is
absorption
fluorescence
10s
as follows : Es, > ET,, Es, >E,, Es, > E, and so on. When a
10-3s phosphorescence
102s
molecule absorbs light radiation, the electron may jump from So to
S1, S, (or) S3 singlet excited state depending upon the energy of
So
the light radiationas shown in Jablonski diagram. For each singlet
excited state there is a corresponding triplet éxcited state, i.e.
Fig. 4.3. Jablonski scheme representing the typical
photophysical.processes in molecules. S, ’ TË; S, ’ T2; S ’ T3, etc.
Most mnolecules possess an even number of electrons and all The molecule, whether it is in singlet or triplet excited state, is
the electrons are paired in ground state. The spin multiplicity of a said to be activated. Thus, An + hy ’ A* where A is the ground
state is given by 2S + 1, where S is the total electronic spin. state molecule and A* is the excited state molecule.
) When the spins are paired (T), the clockwise orientation 4.3.3. Types of transitions
of one electron is cancelled by the anticlockwise
electron. Thus, orientation of other The activated molecules returns to the ground state by emitting
transitions.
tS energy through the following generaltypes of
S=s + S = (1/2) -(1/2) =0
:. 2S +1=1, ie., spii 1. Non-radiative transitions
multiplicity at 1. The molecule is in of any
singlet ground state. Non-radiative transitions do not involve the emission
radiationless
non-radiative or
(ii)) On absorption of a aalations, so these are also known as
suitable energy, one of the paired
electrons goes to a higher energy Tansitions, Non-radiative transitions involve
the following two
level. The spin orientation or
transitions.
 OHOTOCHEMISTRY
PHYSICAL CHEMISTRY-IV (Sem.-Vi)
() Emission spectrum is 239
238
involve th. called Stokes shift. shifted to the higher
(a) Internal conversion (IC) : These transitions
return of the activated molecule from the higher excited
states
s
Itis wavelength region.
The electronic
the first excited states, i.e., Fig.4.4.
transitions during fluorescence is shown in
S, ’ S,; S, ’ S, (or) T;’ T;; T; ’ T, One photon (hv)
The energy of the activated molecule is given out in the for
of heat through molecular collisions. This process is called internal.
conversion (1C) and occurs in less than about 10-l second.
(b) Inter system crossing (ISC) : The molecule may also B
lose energy by another process called inter system crossing (ISC),
These transitions involve the return of the activated molecules from
the states of diferent spins i.e., different multiplicity : S, ’ T,; Reactant Excited Product
S ’ TË: molecule molecule molecule
2. Radiative transitions
Fig. 4.4. Electronic transitions during fluorescence.
Radiative transitions involve the return of activated molecules Eavourable conditions for fluorescence emission
from the singlet excited state S,and triplet state T, to the ground () Energy difference between excited singlet state and excited
state So- These transitions are accompanied by the emission of triplet state is relatively large.
radiations. Thus, radiative transitions involve the following two (ii) Energy difference between ground state and first excited
processes : singlet state is sufficiently large so that possibility of radiationless
(a) Fluorescence : The emission of radiation due to the relaxation process is negligibly small.
transition from singlet excited state S to ground state So is called (b) Phosphorescence : The emission of radiation due to the
fluorescence (S ’ So). transition from the triplet excited state T, to the ground state So is
Characteristic features called phosphorescence (T, ’ So). This transitions is slow and
forbidden transition.
() Absorption of quanta takes place within 10-15sec. Characteristic features
(ii) Singlet excited state is found without changing spin excited singlet state and
orientation. () It occurs only when electrons from
shifted to excited triplet state.
(iii) Vibrational relaxation occurs, due to which molecule are ground singlet state with
shifted to lowest vibrational state with emission of spectra in lk ( ) Finally electrons return to the
emission of radiation.
region. It takes only 10-12 sec. of lower wavelength or at lower
() Phosphorescence occurs observed in fluorescence.
(iv) After vibrational relaxation molecules are returned to the frequencies, much lower than that
ground state with emission of photon in 1R region. This is known state is spin-forbidden, de-excitation from
(iv) As the ground state occurs very
slowly and
as de-excitation process, which is 1000 times slower than relaxation ground
process.
excited triplet state to than a second.
singlet
takes longer time more
 PHOTOCHEMISTRY
PHYSICAL CHEMISTRY-|V (Sem.-Vi) formedbetween excited
240
only when other molecules are called exciplexes,fluorescent molecules and addedforeign241
(v) Phosphorescence is observed sufficiently suppressed
processes, such as quenching. etc. are
deactivating Molecules with heavy
mechanism. Quantum atoms act as quenchers by an
Favourable conditions for phosphorescence of electron spin so
consiexciplex
that derations showthat they facilitateexciplex
change
()Energy difference between excited singlet state
to exciteA degradation via a triplet level. dissociation occurs with energy
'A* + Q ('AQ)* ,3A
triplet state is relatively low.
(i) The probability of radiationless transition from excited triplet Examples of such molecules are xenon,
DA +Q'A+Q
state to ground state is low. and iodides of some rare earth
compounds.bromobenzene, bromides
(6) Energy Transfer Mechanisma
4.3.4. Quenching of Fluorescence
molecula Excited state deactivation by energy transfer is illustrated in
The fluorescence may be quenched, when the excited 45, depicting the HOMO and LUMO spin
collides with a normal molecule before it fluoresces. Durine configurations. The
photo excited molecule called donor starts in the S configuration and
quenching, the energy of the excited molecule gets transferred to has a larger gap between HOMO and LUMO than the
the molecule with which it collides. Fluorescence quenching has nlecule, which acceptor
is initially in the So ground state. As the donor returns
been widely studied both on fundamental phenomenon and on a
to the ground state, the acceptor is promoted to the excited state.
source of information about biochemical systems. These biochemical There are two different mechanisms by which this energy transfer
applications of quenching aredue to molecular interactions that result can take place :
in quenching. Quenching studies can be used to reveal the localisation donor acceptor donor acceptor
of fluorophin in proteins and membranes. Quenching occurs in two (S|) (So) (So) (S;)
ways:
LUMO
1. Internal quenching : Quenching may also occur, when the Forster
molecule changes from the singlet excited state to the triplet excited
state. This phenomenon is called internal quenching.
HOMO * t+
2. External quenching : Quenching may also occur from the
addition of an external substance, which absorbs energy from the LUMO
Dexter
excited molecule.This phenomenon is called external quenching HOMO
External quenching generally occurs by following two mechanisms: HOMO and LUMO
(a) Charge transfer mechanism and (b) Energy transfer mechanism Fig. 4.5.Changes in spin configuration of
during energy transfer.
(a) Charge transfer mechanism donor and acceptor
Forster mechanism :Charge fluctuations in of 10 nm if they
The interaction of excited and ground state of similar molecules of the order
Can influence each other over distances transition in both molecules
leads to the formation of excimers. electronic
ur near resonance of an energytransfer in this
hy
(transition dipole interaction). The probability ofemission spectrum of
A+A ’ A* + A the
’ (AA*) case is proportional to the overlap between acceptor and decreases
When two dissimilar molecules collide, attractive tendencies ad the donor and the absorption spectrum ofThis the
usually greater, depending on polar and polarisable propertie mechanism is responsible
with distance Rlike 1/RO.
Interaction involves some degree of charge transfer. The complexes donor-acceptor
 PHOOTOCHEMISSTRY
PHYSICAL CHEMISTRY-IV(Sem.-Vi)
4.4.1. Primary and 243
242
for the transfer of energy fromthe light-collecting antenna complexes Photochemical
Secondary Processes
secondary processes.reactions
natural photosynthesis. can be
to the reaction centre in classified as Primary and
Dexter mechanism: When donor andacceptor come
close for their orbitals to overlap, the excited electron of the sufdonor
can
be transferred to an unoccupied orbital of the acceptor. At the same
ficiently () Primary Process: The process of the
absorbing process which follows the reaction is the light
equivalence. THhe photon absorbed by a law of
time, an electron of the acceptor moves to the HOMO of the donor.
for donor-acceptor distances smaller excitation. Based on the
photochemical
molecule causes the electronic
than only effective
15 ¢. Aiscommon
This process variant of this process is triplet quenching, relationship
electronic levels, four types of between the lower and upper
state.
primary processes are possible. They
when the donor is initially in the T; are :
4.4. PHOTOCHEMICAL EQQUIVALENCE AND QUANTUM
Type I. In this case, the vibrational energy of the molecule in
YIELD the upper electronic state exceeds the maximum value, which leads
stark-Einsten's law of photochemical equivale may be stated
as :Thein a photochemical reaction, each molecule of the reacting
the dissociation of molecule in its first oscillation.
the reaction Type II. In this case, the molecule is simply excited to the upper
substance absorbs a single photon of radiation causing
photochemical electronic state.
and is activated to form the product". The law of A' absorba
equivalence is illustrated in Fig. 4.6 where a molecule Type III. The molecule is again dissociated as the upper level
a photon of radiation and gets activated. The activated molecule represents an unstable state.
(A*) then decomposes of yield B. That is
A+ hy ’A* Type IV. In this case, stable and unstable upper levels overlap
A*’ B each other. Transition occurs from the lower level to the stable upper
level. During the course of vibration, the molecule is switched over
Over all reaction A + hv B to the unstable one at the point where two levels cross each other
If one mole of A absorbs one mole of photon or one Einstein and the molecule has dissociates. This behaviour is refered to as
of energy E, then the value of E can be calculated by using the predissociation.
expression given below
2-859
(i) Secondary Process : The product of primary process may
E= -x10° kcal mol-! involve in subsequent reactions. These processes are called secondary
processes. The secondary process may involve only one step or
One photon (hv) more than one step. Sometimes, the secondary processes represent
the chain reaction.

HÊ " H +I
Primary process :
A A B Secondary process: H+ HI’H, +>'
I'+>l,
Reactant Excited Product 4.4.2. Quantum Efficiency (Quantum Yield)
molecule molecule molecule
a photochemical reaction is the
Fig. 4.6. Illustration of law of photochemical An important parameter of whichis defined as the number
equivalence-absorption
of one photon decomposes one molecule. quantum efficiency or quantumyield,
 PHYSICAL CHEMISTAY-IV (Sem.-VI)
PHOOTOCHEMIISTAY
244
molecules reacted per
photon of light
absorbed
the number of. AB
Thus
photonis very large.
molecules formed in the overall 245
of light absorbing per reaction
That is,
Number of molecules
reacted Examples High Quantum Yield
=

Number of photons absorbed ..(10) ()Decomposition of HI : The

(1)
reacted, we have broughtabout by the
absorption of light ofdecomposition
less than 4000
of HI is
A. In a
Interms of amount of substance primary reaction, a molecule of HI
absorbs a photon and
followed by secondary stepsdissociates
reacted produce H and I. This is
AIount of the substance
.(11) to as shown
Amount of photons absorbed
=

below.
equivalence, the quantum HI + hv ’ H +I'
According to the law of photochemical
But reaction of low and bit Primary
efficiency willalways be equal to one. H' + HI’ H + I'
high as 10) are known Secondary
quantum yields (as low as 0-04 and as
4.4.3. Cause of High Quantum Yield 2HI + h ’ H,+ h Overallreaction
than one molecule
When one photon decomposes or forms more
high. The main reasone In the overall reaction, two molecules of HI are decomposed
the quantum yield > 1and is said to be
of high quantum yield are : for one photon of light absorbed. Thus the quantum yield is 2.
(a) Reactions subsequent to the primary reaction : One (2) Hydrogen -chlorine reaction : This is a well known
photon absorbed in a primary reaction dissociates one molecule of example ofaphotochemical chain reaction. Amixture of hydrogen
the reactant. But the excited atoms that resulted from the primary and chlorine is exposed to light of wavelength less than 4000 A.
reaction start a subsequent secondary reaction in which a further The hydrogen and chlorine absorbs a photon and dissociates into
molecule is decomposed. two Cl atoms. This is followed by the secondary reactions as given
AB + hv ’ A+B Primary below :
Primary reaction Cl, + hv ’ 2CI ..()
AB + A ’ A, + B Secondary
It is clear that, one photon of radiation decomposes two molecules ’ HCI+ H ..(i)
Cr +H)
.

of the reactant; one in the primary reaction and one in the secondary Secondary reaction
reaction. Hence quantum yield of the overall reaction is 2. |H+Ch HCI+ CI' ...(ii)
(6) Chain reaction : When there are two or more reactant, a
self-propagating chain reaction.
molecule of one of them absorbs a photon and dissociates (primary The steps 2 and 3 constitute a
reaction). The excited atom that is produced starts a secondary for a photon of light is
reaction chain. The number of HCI molecules formed
of the reaction varies from 10* to
A, + hv ry high. The quantum yield
’ 2A Primary 106.
A+B, ’ AB +B Secondary reaction Decomposition of HBr is brought
(S)Decomposition of HBr :region. The primary photochemical
B+ A, ’ AB + A Chain about by the radiation in the UV
This reaction chain continues to form two Step can be written as
molecules each time:
 PHYSICAL CHEMISTRY-IV (Sem.-VI PHOTOCHEMISTRY
246

[HBr] This shows that

’ H, + Br (i) rate = I¡bs = kË
absorpt ion
hv
HBr decomposition of two of one 247
therefore two. of photon
molecules HBr, the leads to the
This is followed by secondary process quantum effTiciency is
4,4.4. Causes of Low
H+ HBr H, + Br (ii) rate = k, [H) (HBr]
The main reasons of low
Quantum Yield
and Br + Br ’ Br, (iii) rate = k; [Br]² quantum yield are
(a) Deactivation of
Possibility of other elementary reaction of the type molecules in the
primary reacting molecules : The excited
process
get opportunityto react. This is
may be
deactivated before they
Br + HBr- -’Br, + H
molecules or by flourescene.
caused by collisions with some insert
H+ HH, A + hy ’ A*
Br + H- >HBr A* ’ Activation
A + hv
is ruledout as they involve either high activation energy or require (6) Occurrence of reverse of primary reactionFlourescence
: Here the
third body collision. The overall reaction is therefore obtained by nrimary reaction generally yields a product and it
adding reaction (i), (ii) and (iii) reaction and giving back the reactant molecules.undergoes a reverse
2HBr ’H, + Br, 2A
The overall rate of this reaction is given by Ag
The reverse reaction proceeds till the equilibrium state is
-dHBr] reached.
dt = Labs t k, [H] [HBr] ...(iv)
and the rate of formation of H atom is (c) Recombination of dissociated fragments : In a primary
process the reactant molecules may dissociate to give smaller
d[H] fragments. These fragments can recombine to give back the reactant.
dt = Iabs - k, [H] [HBr]
(AB) + hy’ A+B
In the steady state d[H] =0
dt A+B’ (AB)
labs - kz [HBr] [H] =0
Examples of Low Quantum Yield
anthrance Cj40
Labs (1) Dimerisation of anthrance : When dianthracence
dissolved in benzene exposed to UV, it is converted to
or
[H]= k[HBr]
Substituting the value of [H) in eq. (iv), we get CzgH20 ’ CzgHzo
2C14Ho+ hv foundto be
should be 2but it is
the quantum yieldflourescence
0-5. Obviously,
abs emission and reverse
ky[HBr] =labs + abs 2abs It due to the deactivation by
reaction.
 PHYSICAL CHEMIST
STRY-IV (Sem.-Vi) PHOTOCAEMISTRY
248
(2) Combination of H, and Br; : When a mixture of H, and Solved Problem 8.
formed. The possible steps are WAvelength 1x 104 moleWhen irradiated 249
with light of 5000 Å
Br, is exposed to light, HB7 is of a
Br, +hv2Br"
mAnyphotons are
efficiency is 10-00. absorbed
during substance is decomposed.quantum
the reaction if its How
Primary reaction HBr +H*
Br' +H, ..<) Solution :Quantum
efficiency of the reaction = 10-00
No. of moles decomposed =1×104
H+Br ’ HBr + Br
..(ii) Ste of molecules
decomposed = 1x104x6-02x1023
Secondary reactionH+ HBr ’ H, + Br =6-02×1019
Br + Br' Br, ..(v) No. of molecules
No. of photonsdecomposed
=

The reaction (ii) is extremely slow. The reactions (ii), (iv) and absorbed
(v) depend directly and indirectly on (i). So most of the Br atoms 6-02x 10!9
produced in the primary process recombine to give back Br No.of photons absorbed
molecules. So HBr molecules obtained per quantum is extremely
small.
.:: No. of photons absorbed = 6-02 x109 = 6-02 x 1018
Solved Problem 7. When a substance A was exposed to 10
light, 0-002 mol of it reacted in 20 minutes and 4 seconds. Solved Problem 9. When propionaldehyde is irradiated with
In the same time A absorbed 2-0 x 10° photons of light per lieht of = 3020, it is decomposed to form carbon monoxide.
second. Calculate the quantum yield of the reaction.
Solution : Number of molecules of A reacting CH,CH,CHO+ hv ’ CH,CH, + CO
The quantum yield for the reaction is 0-54. The light
= 0-002xN = 0-002 x 6-02 x 1023
energy absorbed is 1500 erg mol in a given time. Find the
Number of photons absorbed per second amount of carbon monoxide formed in the same time.
= 2-0x106
1-196x106 erg mol-!
Solution : One einstein E=
one
ei n t e n

Number of photons absorbed in 20 minutes and 4

seconds
= 2-0x10 x 1204 1-196x10!ó
when 2 = 3020Å, One einstein
Quantum yield = No. of molecules reacted 3020
No. of photons absorbed
15000 x 3020
0-002 x6-02 x1023 or. 15000 erg mol of energy = 1-196x10.6
= 5-00 x 10!1
2-0x10° x1204 =3-78x10- einstein.
 PHOTOCHEMIISTRY
PHYSICAL CHEMISTRY-IV (Sem.Vi)
250 The possibility of;free rotation facilitates cis-trans 251
formed andit can be demonstrated as follows :
No. of mole of CO isomerisation
absorbed = 0-54
But = No. of einsteins H
H

of CO formed. HOOC COOH kcis

Hence, the amount 2-04x10-9 Maleic acid
HOOC cOOH
= 0-54 x 3-78 x 10= moles
Solved Problem 10.
Aradiation of
253 nm incident on HI
decomposition of 1·85x10-%
mole per 1000
cal
H, ,COOH
h H,
1 0OH
results in the c=C

of radiant energy. CCalculate

the quantum efficiency
)
of the HOOC H ktrans
6-023x10,b= 6"62x10-3 J HOOC H
process. (Given N, = Fumaric acid

radiation =253 nm = 2-53x10-7, Starting from any given configuration, the

Solution: Wavelength of
= 1-85x 10-2 mol
ieomer can be produced on photoexcitation bycorresponding rotational
suitable wavelength.
No. of molesdecomposed Aphotostationary equilibrium is established, differing from the
and 1000 cal=4184 J thermodynamic equilibrium of the ground states.
A5, PHOTOSENSITIZATION REACTIONS
Energy per quantum
In some cases, reactant molecules are not sensitive enough to
6-62 x1034 x3x10° >x6-02x1023 excess photochemical reactions but they undergo photochemical
2-53 x10-7 reactions in presence of particular foreign substance. The foreign
substance is known on photosensitizer. At the initiation step,
= 4-728 x 10 J molH photosensitizer molecule, also known as donor, absorb visible-light
and is shifted to singlet excited state. Through ISC, the molecule
Number of einstein of the given energy of 4184 J further shifted to triplet excited state. But the lift time of this triplet
energy
state is too short. The triply excited molecule transfers the
4184 energy transfer the
= 0-0885 to the acceptor molecule (reactant). During the (singlet). The
4-728 x 10 triply excited molecule go back to the ground state
1-85 ×10mol Overall mechanism is given below :
Hence 0-208 D+ hy -
0-0885 einstein
D ³D
4.4.5. Cis-trans Isomerisation of Maleic Acid to Fumaric Acid ’ D +'A
D+A
The lowest excited state of malejc acid results from excitatiol ’ Products.
of a melectron into an antibonding Tr*-orbital. In this state, e BA
of naphthalenein
bonding effect of r orbital is cancelled by antibonding effect 0 Forexample considerthe phosphorescence
benzophenone acts as
n* orbital and the resulting C-C bond is effectively a single bond. benzophenone, where the (acceptor).
Consequently, free rotation around C-C bond becomes possible. ence of naphthalene as the reactant
photosensitizer (donor) and
 PHYSICAL CHEMISTRY-IV (Sem.-V
PHOTOCHEMISTAY

252
is given below. dioxide and water occuring in plants in the presence of 253
mechanism of the process an example of
The proposed is
also
molecule. Several phot osensi ti chlorophyl
ofzation. Chlorophyll is a complex
modifications
organisms.chlorophyll occur among plants
ISC other photosynthetic
nHsC7--&
hv and All
H_C6 TËtt havechlorophyll a. Accessory
dand e in algae and
photosynthetic
pigments include chlorophyllorganisms
6 (also
So t . protistans), xanthophyl ls and
carotenoids.
Chlorophyll + hv ’
Energy
6nCO,+5nH,0+(Chlorophyll)
(Chlorophylly*
Transfer
So tt ’ (CH;o0s), +6n0,
Carbohydrate
iDPhotography : The photographic film has a
Phosphorescence emulsion consisting of colloidal coating of an
photosensitizers in gelatin. When suspension of silver bromide and
it exposed to light no
Sott ohange occurs but when the exposed plate is immersedobservable in dilute
pyrogallic acid solution, the exposed parts react with it. That is how
reaction ilyer grains are formed on the plate and unreacted silver bromide
Fig. 4.7. Mechanism of Photosensitization
is removed by dissolving it in hypo solution to get negative of the
4.5.1. Examples of Photosensitized Reactions flm.
(a) Reaction between H, and 0, : This reaction is This negative plate is then kept over sensitized emulsion plate
photosensitized by mercury vapour. The product is hydrogen peroxide of silver halide and the process is repeated again to get positive
H,02 point.
Hg + hv’ Hg* Primary absorption
(e) Photosensitized isomerisation of cis-2-butene to trans
Hg* + H,’ 2H" + Hg Energy transfer 2-butene: SO, photosensitized the isomerisation of cis-2-butene
H+ O2 into trans-2-butene upon 253.7 nm irradiation
HO,
Reaction SO, + hy
HO, + HO, ’ H,0, + O,
SO,* + cis-2-butene SO, + cis-2-butene*
(b) Reaction between H, and CO : Mercury vapour is useo ’ trans-2-butene*
as photosensitizer in this reaction. cis-2-butene*
trans-2-butene* trans-2-butene
Hg + hv’ Hg* Primary absorption
Hg* + H, ’ 2H + Hg Energy transfer 4.5.2. Chemiluminescence
radiation
H+ C0 HCO Chmiluminescence is the generation of electromagnetic
reaction. Thus,
chemical
ght by the release of energy froma aphotochemical reaction. As
HCO + H, ’ HCHO + & is the reverse of
2HO Reaction chemiluminescence
the emission occurs at ordinary temperature, the emitted radiation
chemiluminescent reaction, the
HCHO + CO is also "cold light". In a
(c) Photosynthesis : Synthesis of carbohydrates from carbon knownas
 PHOTOC
CHEMISTRY
PHYSICAL CHEMISTRY-|V (Sem.
254 singletexcited state
!Ar* is
energy released during the chemical reaction makes the Produp
molecule electronically excited. The excited molecule then
iectivated by the
emission of fphotormoed.n h.The excited state can255be
reactemiionsts
radiation, as it returns to the ground state. Chemiluminescent 4.5.3. Bioluminescence
can be grouped into three types : Bioluminescence is an
interestby itheng chemical
(i) Chemical reactions using synthetic compounds and usuali.nsDicuous visible light emitted
reaction
involving a highly oxidized species such as a peroxide are several could be found inluminescent orwherganiesbyms.a
history of this
termed chemiluminescent reactions.
commonly
The phenomenon
ond
andparticularly marine
(i)) Light-emitting reactions arising from a living organism, sut organisms share envi
similar ro nment s. ter eallstriathel, freshwater
Yet, almost
lurminescence emission refer chemical lumiinnousthe
as the firefly or jellyfish, are commonly termed to as component s invol v ed
bioluminescent phenomenon is
enormousl luciferin and lucisea,ferase. ParticularBy
bottom yof the
reactions. this
aphotic Zone to till the common in deep
especial y from
(iii) Light-emitting reactions which take place by the use o6 sea.
This emission could be
electrical current are designated electrochemiluminescent the major phyla which
Over all found
reactions. few groups refer to plants, birds,represent at least one
genus, except
Examples phenomenon COvers diverse hues, amphibians, and mammals. This
(a) The oxidation of ether solution of magnesium p-bromophenv The proteins and genes involved in thereactions and emission
paterns.
bromide gives rise to chemiluminescence, the greenish glow that have awide importance in medical andluminescence of some organisms
accompanies the exposure of solution to ait, being visible in day light nthis review we shall devote to talk verybiotechnological applications.
briefly abot biols
(b) Glow of phosphorous and its oxide, in which the oxide in of different organisms, current aspects, and applications.
its excited electronic state emits light. Bioluminescence emission could be found in different patterns as
(c) When pyragallol is oxidized by H,0,, chemiluminescence flashes (fireflies, squids, odontosylis), continuous giow(bacteria, fungi),
is produced. blinking (bacteria),wavy (sea pansy, renilla), and switched on and off
(d) The glowof fire flies is due to the chemiluminescence of a system (angler fishes). Interestingly some bioluminescent organisms
protein (luciferin) oxidation by oxygen in presence of an enzyme such as ophiuroids and earthworms emit luminescence in presence of
(luciferase). stimulating chemicals like KCI.
Mechanism There are five different luciferins responsible for the bioluminescence
Mechanism of Chemiluminescence can be explained by of most of the known bioluminescent organisms. They are bacterial
luciferin (related to
luciferin (a derivative of riboflavin), dinoflagellate(requires
considering anion-cation reactions. For example, interaction between luciferin ATP for
the aromatic anions (Ar) and cations (Ar). the chlorophyll structure), firefly common, found in several
coelenterazine (extremely
Ar + Ar’'Ar* + Ar bioluminescence),
species), and vargulin (found in
ostracods). However, emission
discovered.
'Ar* ’ Ar + hy luminescent organisms are yet to be lumazine
mechanisms of many jellytishes)and
such as GFP(in known to be involved
The aromatic anion (Ar) contains two paired electrons in the Noticeably fluorescent proteins.
phosphoreum)arealso
bonding molecular orbital (BMO)and one unpaired electron in " protein (in photobacterium
In emission of intense luminescence. are the
antibonding molecular orbital (ABMO). The ABMO of the arom currently being practiced
cation (Ar") is empty. When the electron is transferred from t applications that production, whole-
and
ABMO of the anion (Ar) to the ABMO of the cation (Ar); the Important autoluminescentpplantsfor light
development of
 PHYSICAL CHEMISTRY-|V (Sem.-Vi)
256 PHOTOCHEMISTAY
cell biosensors for detecting various toxicants. Besides, cloning studies
their Give an example for
of different luminescent organisms and
photchemiosensilumitinzesaticoence.n?
of luciferases
proteins such as the well-known green fluorescent protein (GFP) have fluorescent 20

21.
What is meant by
257

got a wide importance in bioluminescent Imaging (BLI) to studv the Give an example for
interaction of infectious microorganisms with living cells.
23. Explain the applications of photosenvitized reaction. in
QUESTIONS
SECTION-A
24.What is flash photohysis?
25. What is meant by inter-syste-
photosensitization photography.
26. What is meant by internal
crossing?
1. What is a photochemical reaction ? conversions?
2. Give two examples of photochemical reactions. What is quenching of fluorescence?
3. Give any two differences between photochemical and thermal reactions
4. State Beer-Lambert Law.
1
SECTION-B
Explain photochemical equivalance and quantum
5. Give mathematical forn of Beer Lambert law.
Discuss the reasons for high and low quantum yield.efficiency.
6. Define molar absorption coefficient.
2 Calculate the energy
7. State Grothus-Drapper law. available on absorption of 1-5 Einstein of aradiation
of wavelength 5560¢.
8. State Stark-Einstein law. [Ans. 3-22x 105J]
4 Write a short note on flourescence.
9. What is meant by primary process isa photochemical reaction?
5. Write a short note on phosphoresence.
10. What do you understand by the term secondary process in a
photochemical reaction. 6. What are photosensitized reactions? Give examples.
11. Define quantum yield of aphotochemical reaction. 7. Explain with a specific example, explain photochemical reactions with high
12. What ar e the different reasons of high quantum yield of photochemical quantum yield.
reaction. 8. Distinguish betwen photochemical reactions and chemiluminescence.
13. Give any two reasons for the extremely low quantum yields of some Draw Jablonski diagram and explain different transitions.
photochemical reactions.
14. Give one example each for photochemical reactions of high SECTION-C
and low quantum yield.
quantum yield
equivalence. Give
15. What is flourescence?
l. State and explain stark-Einstein law of photochemical
the explanation for low and high quantum yields.
16. What is phosphorescence? various type of transitions.
Draw the Jablonski diagram and explain the
17. Which type of transitions are occur along with phosphonesence and fluoresence by giving
emission? phosphorescence ()Distinguish between
importance to their mechanisms.
18. What is meant by
chemiluminescence? (b) Write a note on photosensitization.
19.
"Chemiluminescene is regarded as the reverse of photochemical reaction.
Justify this statement.