PHOTOCHEMISTRY 2/15

every absorbed photon. Hence, the quantum vield is less than one. The concept of quantum
vield helps us to understand the nature of
secondary processes.
Note
The quantum yield is dependent on the intensity of light.
2.07.1. Primary and Secondary Processes
Photochemical reactions generally involve two processes. These are known as primary
Drocess and secondary process. These can be detailed as follows:
1.
Primary processes. This step of photochemical reaction follows the law of photochemical
equivalence. In this step one molecule absorbs one photon of light and gets excited to a higher
energy state. This can be schematically given as follows:
A+hv A]
(Activatedmolecule)
The activated molecule may undergo a chemical change, it may associate or dissociate
itself to form atoms or free radicals. It may lose its energy by collisions with other molecules or
it may undergo phosphorescence or fluorescence.
2. Secondary processes. The species (atoms, molecules or free radicals) formed in the
primary process may undergo further reactions which are called secondary processes.
The secondary processesmayinvolve one or more than one step. Sometimes, the secondary
process initiates a chain reaction. Such reaction may result in very high or very low
vields. Both the primary and secondary processes carn be shown in the following examplequantum
2H1-lghtH+l2
Primary Process HI H+I
Secondary Processes H+I H2+1
2.08. REASONS FOR LOW AND HIGH QUANTUM YIELD
The quantum yield may be as high as 10 or as low as 0.2 for many photochemical reactions.
The reasons for low and high quantum yields are as follows:
1. Low quantum yields. The quantum yield will be less than unity only when less than
one mole of reactant reacts on absorption of one einstein of energy. As lesser number of moles
of rectant undergo reaction than predicted by Stark-Einstein law for absorption of one einstein
of energy absorbed, therefore, the quantum yield is less than one. This may be due to number
of reasons as follows
() The activated molecule may simply emit the absorbed radiation and get deactivated.
(i The excited molecule may collide with surrounding non-excited molecules and lose
energy in the form of heat.
(a) The atoms/radicals formed in primary step may recombine to form original molecules
(ro) The excited molecule may react with other molecules to produce unwanted products.
() The excited molecule may emit energy in the form of fluorescence or
phosphorescence.
(T) The secondary process may involve a reaction which forms reactant as one of the
products.
(290) The primary photochemical process may be reversible.
2. High Quantum yields. The law of
photochemical equivalence fails in reactions where
the number of reactant molecules undergoing
reaction
by absorption of one of
quantum light
 2/16 CHEMISTRY (B.SC. , Sem.v) Jammu U PHOTOCHEMISTRY
DERN APPROACH TO PHYSICAL
1S more than one. The quantum yield will be high if more than one mole of reactant molecules react on Secondary processes
absorption of one einstein of energy. High quantum vield is explained on the basis of reactions (i) H+HI-
taking place in secondary processes. This may occur when the primary process proauces eXCIted (11) I + HIEndotm
series of chain reactions
may initate
a
tormed in primary Exoth
dalcals process
iii) H + H
y aosorbing only one quantum of radiation. several reactant molecules undergo Chemical (io) I+I
Hcthas quantum
. Or example, a photochemical reaction between H, and Cl, to form
yield of the order of 10 to 10 (o) H+I Exot
ihe quantum yields for Out of these second
some photochemical reactions are given in labie at ordinary temperature.
Table 1:Quantum yields of some photochemical reactions formed in i
Reaction Quantum yield (p) the products
Wavelength of light reactions which take plac
used (nm) the overall rea
procesS,
HI + hv
Reactions in which quantum yield
HI +H
is a
simple integer I+I
CH,COCH, C2 H, + CO 300 The overall photo
SO+Cl, SO,Cl, 420 2HI +hw
H,S-H, + S Thus absorption -
208
2HBr H, +
Br2 207 253 Therefore, the quantuw
In case of HBr a
2HI- H +I2 207 282
iodide molecule and
30,3 O 170 190
thatthe mechanisme
Reactions with high quantum yield
HCl22HCI 400 436 above.
104 106
CO+ Cl COCl 400 436 103 (b) Photochemical
Reactions with very
1. Combinatio-
low quantum yield
H2+ Br,2HBr 510 0.01 The photoche
2 N H N , + 3H 210 0.25 i.e. 0.01 at ordinary
CHCHO>CO+CH 310 n5 dissociate bromin.
2NO,2NO+O2 405 the reaction is as
2.09. SOME EXAMPLES OF PHOTOCHEMICAL RE NS Primary proce
A photochemical reaction involves two processes viz p
Br,+hv
already explained. The quantum yield of the primary process
process as Secondary pr
equal
with the law of photochemical equivalence. The seconda es re
CCordance Br +H
reactions. Few photochemical reactions and their mechani
thermal
scrib H+B
(a) Reactions in which quan yield is a simple inte At) H+H
(i) Photochemical decon on of hydrogen iod (io) Br +E
emic
of HI has been carried out us t of wavelength 2 The tior In step ()-
this reaction is nearly 2. The g mechanism ha sed rming hydro
decomposition of HI; molecule form
i) and (ii) are =
Primary process
HI +h of the reaction
reason for lov=
Hydrogen iodide molecule a ohotor Reactior
excited iodine atom. The primary } Therefore, the
atoms in reac