WEEK 3 L1

PHOTOCHEMISTRY
PRESENTED BY
Dr Shaista Taimur
DEPARTMENT OF CHEMISTRY
Fatima Jinnah Women University
Rawalpindi
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Disclaimer:
“In preparation of course materials different online sources in the
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etc) is prepared and delivered only for educational purposes and is not
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acknowledged where applicable. The views expressed are presenter’s
alone and do not necessarily represent actual author(s) or the
institution.”
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At the end of the lecture, you will be able to:

• Understand Einstein’s law of photochemical equivalence

• Describe Efficiency of photochemical processes
• Understand Primary processes and secondary processes
• Explain Primary Quantum Yield and Overall Quantum Yield
• Apply knowledge to some examples and compute
numerical problems
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SECOND LAW OF PHOTOCHEMISTRY
STARK-EINSTEIN LAW OF PHOTOCHEMICAL EQUIVALENCE
• It was put forward by Einstein (1905) and Stark (1908)
• Statement: “Every atom or molecule that takes part in a photochemical reaction absorbs one quantum
of the radiation to which the substance is exposed”
OR
The primary act of light absorption by a molecule is a one - quantum process. That is, for
each photon absorbed only one molecule is excited.
• If v is the frequency of the absorbed radiation, then the energy absorbed by each reacting atom or
molecule is one quantum i.e. hv where h is Plank’s constant.

E=hv
• The energy absorbed by one mole of the reacting molecules will then be given by

𝑵𝒉𝒄
E=Nh v =
λ
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Einstein and its numerical value
•The energy possessed by one mole of photons (or the energy absorbed by one mole of
•the reacting molecules) is called one Einstein.
Numerical value of Einstein in different units
(a) In SI units, N = 6.022 x 1023 mol-1 , h = 6.626x10-34 Js and c=3.0x108 m/sec

𝑵𝒉𝒄 𝟔.𝟎𝟐𝟐𝒙𝟏𝟎𝟐𝟑 𝒙𝟔.𝟔𝟐𝟔𝒙𝟏𝟎−𝟑𝟒 𝒙𝟑.𝟎𝒙𝟏𝟎𝟖

E= = J Einstein-1
λ λ(𝒎)

𝑵𝒉𝒄 𝟎.𝟏𝟏𝟗𝟕 𝑵𝒉𝒄 𝟏𝟏.𝟗𝟕𝒙𝟏𝟎−𝟓

E= = J Einstein-1 E= = kJ Einstein-1
λ λ(𝒎) λ λ(m)
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Einstein and its numerical value

(a) In CGS units, N=6.022 x 1023 mol-1, h=6.626 x 10-27 erg sec and c=3.0x1010cm/sec.

𝑵𝒉𝒄 𝟔.𝟎𝟐𝟐𝒙𝟏𝟎𝟐𝟑 𝒙𝟔.𝟔𝟐𝟔𝒙𝟏𝟎−𝟐𝟕 𝒙𝟑.𝟎𝒙𝟏𝟎𝟏𝟎

E= = ergs Einstein-1
λ λ(𝒄𝒎)

𝑵𝒉𝒄 𝟏𝟏𝟗.𝟕𝒙𝟏𝟎𝟔 𝑵𝒉𝒄 𝟏𝟏𝟗.𝟕𝒙𝟏𝟎𝟔

E= = ergs Einstein-1 E= = cal Einstein-1
λ λ(cm) λ 𝟒.𝟏𝟖𝟒𝒙𝟏𝟎𝟕 λ(cm)
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Quantum Yield or Quantum Efficiency

• The quantum yield is a measure of how efficiently the absorbed photons are utilized.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔

φ=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑞𝑢𝑎𝑛𝑡𝑎 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑

φ=1
φ<1
φ>1
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PHOTOCHEMICAL
PROCESS

PRIMARY PROCESS SECONDARY PROCESS

Light quantum of energy hv is absorbed by
the molecule to form excited molecule
This process follows law of photochemical
equivalence
• The products of the primary process like atoms,
molecules or free radicals react further to give
final product.
• Sometimes chain reactions can also e initiated.
• Deactivation of excited state
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Reasons of high quantum yield Reasons of low quantum yield

• The activated molecules may innitiate a series of • The excited molecules may be deactivated by
chain reactions e.g. H2 and Cl2 combine to give converting their energy into KE of other molecules
φ of order 106. (in heating effects)

The φ depends upon the length of chain propagating IC + ISC

steps.
• The excited molecules may get deactivated
• If the secondary photochemical reaction is through fluorescence and phosphorescence.
exothermic, the heat of the reaction may activate
• The dissociated fragments may recombine to form
other molecules thereby causing them to react.
the original molecule.
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Irradiation of acetone with 313 nm light (3130 Å ) gives a complex mixture of products, as shown in the
following diagram. The quantum yield of these products is less than 0.2, indicating there are radiative
(fluorescence & phosphorescence) and non-radiative return pathways (green arrow). The primary
photochemical reaction is the homolytic cleavage of a carbon-carbon bond shown in the top equation.
Here the asterisk represents an electronic excited state
Several secondary radical reactions then follow (shown in the gray box), making it difficult to assign a quantum
yield to the primary reaction.
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FORMULA:
𝑛𝑅 . 𝑁𝐴 ℎ𝑐
𝜑=
𝐸𝑇 𝜆
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NUMERICAL:
Absorption of UV radiation decomposes acetone as
follows

The quantum yield of the reaction at 280nm is 0.2.

The sample of acetone absorbs this radiation at
the rate of 7.5x10-3 Js-1. Calculate the rate f
formation of CO.
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HOME ASSIGNMENT
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