Photochemistry

313 C
 Assistant Prof. Abdelreheem A. Saddik
Doctor of Materials Science
Dep. Chem., Fac. of Sc., Assiut University

Office: Chemistry Building (B), 1st Floor,

Room No.104
Ethics:

 Mobiles should be silent ( please check)

 Questions only with permission
 Side discussions are not allowed
 Entrance & leave should be quite and
organized

Thank You
 Sciences

Applied Humanity

Basic

1. Mathematics. 4. Geology.
2. Physics. 5. Botany.
3. Chemistry. 6. Zoology.
 Chemistry

- Physical Chemistry - Organic Chemistry

- Inorganic Chemistry - Biochemistry
- Analytical Chemistry - Several Others
Course Title : Photochemistry.

Course code: 313 C

Credit hours: 1.5 Credit Unit.

Pre Requisite: 212 C

Supplemental Material:
Lectures Note & Associated References
1- To understand the basic principles
and types of photochemical reactions.
2- To ensure that students have a good
knowledge about photoenergy and on the
role and significance of photochemistry
for human being, now and in future.
Contents
1- Introduction.
2- Light Sources.
3- Light Filters.
4- Solar Energy.
5- The Spectral ranges of light.
6- The fate of excited states:
a) Physical processes (Jablonski diagram).
b) Chemical processes.
7- Ground state and Excited states.
8- Quantitative measurements (Quantum yield).
 9- Energy transfer.
10- General Types of Photochemical Reactions:
a- Photo-reduction Reactions.
b- Photochemical Reactions of ethenes.
polyethenes and ethynes.
c- Photoisomerizaion of benzenoid compounds.
d- Photooxidation.
e- Photochemical aromatic substitution.
f- Photochemical Fragmentation.
11- Photochromism.

12- Photochemistry of Vision.

13- Microwaves in Organic Chemistry.

a) Introduction.
b) Principal Mechanisms for Interaction
with Matter.
c) Microwaves Assisted Reactions.

14- References.
1. Modern Molecular Photochemistry, N. J.
Turro, The Penjamin / Cuminings Pub. Co.,
Inc. London, 1978.

2. Advanced Organic Chemistry, J. March, Mc

Graw-Hill, Tokyo,1977.

3. CRC Handbook of Organic Photochemistry

and Photobiology, W. M. Horspool and F.
Lenci., CRC Press, London, NY, 2003.
Periodicals, Web Sites... Etc
www.google.com.
www.sciencedirect.com.
 PHOTOCHEMISTRY

 Photochemistry is the study of reactions

caused by absorption of light.

Chemical changes induced by Sunlight :

1- The miracle of Photosynthesis, on which all
life depends, is fundamentally a chemical
reaction between CO2 and H2O effected by
Chlorophyll, the pigment responsible for the
color of green plants.
 Sunlight
6CO2 + 6H2O C6H12O6 + 6O2
Chlorophyll
Glucose

2- The response of an eye to light is triggered by a

photochemical change of the pigment rhodopsin in
the visual rods.

3- Less beneficial photochemical changes are

experienced in the form of sunburns and skin
cancers, the latter affliction being especially prevalent
among fair-skinned people living in tropical regions.
4-Photoreactions: For example, the
Cannizzaro research work in
photochemistry was reported in the early
19th century .

2 –CHO
Base
-COO- + CH2OH

Photoreactions was long considered by

many organic chemists as a small branch
of their field until relatively recently.
 Theory of Photochemistry.
 The fundamentals of photochemistry are
remarkably simple.
 A molecule becomes energized to an excited
state by absorption of a photon of light and
undergoes a chemical reaction while still in that
excited state.
 The difference between Photoreactions and
ordinary Thermal reactions lies in the fact that in
photochemistry individual molecules are
promoted to highly excited forms without
immediate effect on surrounding molecules.
 In a Thermally activated reaction energy
entering the system in the form of heat is
apportioned among all of the molecules in the
system according to statistical principles.

 The Selective Excitation of individual

molecules in photochemistry, unique
character, is a little like being able to touch a
match to a single straw in a haystack and
burn it without having the fire spread to the rest
of the stack.
Another characteristic of photochemistry
arises from the fact that the chemical
changes occur in energy-rich molecules.
Reaction is usually accompanied by loss of
energy from the excited species.

This is in sharp contrast to thermally

activated reactions in which activation
energy is gathered in small bits from the
environment.
Figure 1 Absorption spectrum of benzophenone in ethanol solution
 Light Sources and Light Filters
 Although photochemical experiments are usually
easy to perform, a number of theoretical and
practical requirements have to be met.

 The major part of the 1st section consists of some

technical data of commercially available gas
discharge lamps.
 Also included are some rather marginal remarks
on other artificial light sources and on sunlight.

 The 2nd section contains some data on Filters.

 1. Light Sources
More emphasis will be laid on a survey of
commercially available gas discharge
lamps rather than on treating all possible
light sources.

Only closed lamps will be considered, the

intrinsic properties of which (form,
dimensions, and staring properties) permit
mounting within the reaction vessel.
Although most of the lamps mentioned below
are constructed for illumination, photocopying,
and sterilization purposes, they may well be
used for preparative photochemistry.

The main spectral region which has to be

considered is the range 250 – 600 m.

Figure 1, a-h, shows typical emission spectra

of the lamp.
Aided by these data, one should be
able to select the lamp most suitable for his
problem.
 Also, One should keep in mind that the spectral
energy distribution not only depends on the kind
of vapor but also on the pressure employed.

 Generally Low-Pressure lamps show few, sharp

lines (resonance lines).
 With High-Pressure lamps, new lines appear at
longer wavelengths and an increasing
broadening of the lines can be observed.
 a) Low-Pressure Sodium Vapor
Lamps

Low-pressure sodium vapor lamps

emit nearly monochromatic light of
589 m (fig.1a) with a very high yield.

The average lifetime is about 5000

hours with 1000 starting process
 b) High-Pressure Sodium Vapor
Lamps

A high-pressure sodium lamp has recently

been put on the market by General Electric
Co. LU-400. The lamp is delivered with a
ceramic arc-tube in an evacuated glass bulb.
The spectrum of this lamp shows several
broadened lines (fig. 1, b).
 c) Low-Pressure Mercury Lamps

Low-pressure mercury lamps (0.005-0.1 mmHg)

show emissions mainly at 253.7 m (fig. 1, c).

The fraction of light of a longer wavelength

strongly depends on the working pressure and
varies in the various low-pressure.
 - If Quartz is used for the construction of
the arc tube, the lamps also show ~ 8%
radiation of 185 m,
- Lamps with a Vycor tube do not emit this
wavelength, at which ozone is already
formed.

arc tube
 d) High-Pressure Mercury
Lamps
 High-pressure Hg lamps (1-10 atm.) show,
besides a weak continuum emission, a typical line
spectrum (fig. l, d).
 Quite frequently these lamps will also be
designated as medium-pressure mercury lamps.

 High-pressure Hg lamps with Halide additives

show, besides the mercury lines, the lines of the
metals added as their halides.
By employing a suitable mixture of metal
halides (mostly iodides) a more uniform
distribution of energy (resembling daylight)
and higher light intensities can be
achieved.

The following metal iodide lamps are

available, the predominating emission
range being given in brackets:
 TlI (320 – 380, 530-540 m)
NaI (~ 590 m)
CdI2 (300-360, ~ 640 m)
ZnI2 (~ 330, ~ 635 m)
InI3 (270-280, 300-330, ~ 410 m)
MgI2 (~ 280 m)

While the normal lifetime of high-pressure

mercury lamps with halide additives is 800
hrs, that of lamps containing MgI2 or ZnI2
is only 400 hrs.
 e) Super-high-Pressure Mercury
Lamps
Mercury lamps with working pressures of
up to 200 atm are designated as super-
high-pressure lamps, they are occasionally
also termed just high-pressure lamps.

They show a much more compact arc than

the aforementioned high-pressure mercury
lamps of the same output. Their emission
spectrum(fig.1 e) shows a stronger
continuum and broadened mercury lines.
 f) Super-High-Pressure Xenon-
Mercury Lamps
 Super-high-pressure xenon-mercury lamps also
have a very short arc with extremely high
brightness.

 The spectrum (fig. 1, f) shows mainly the mercury

lines with very high intensities down to 290 m.

 The luminous flux is constant within 15 minutes

after starting of the arc.
 g) High-Pressure Xenon Lamps
 High-pressure xenon lamps(working pressure 1- 50
atm) emit a continuum spectrum, in the visible
region quite similar to the daylight (fig. 1, g).

 The strong emission lines of xenon lie in the

infrared region 800 - 1000 m.

 In the UV the spectral energy distribution

corresponds largely to that of extra-terrestrial
sunlight, the intensity decreasing with decreasing
wavelengths.
 h) Sunlight
The use of Sunlight (fig.1,h) as a light source
involves certain difficulties :

1- Low intensities, especially in the short

wavelength region

2- Low reproducibility in intensity due to changes

in, for example, the angle of incident radiation
during the day and during the seasons of the
year.
3-Besides, in insulation experiments
precautions, have to be taken to exclude
thermal reactions which might otherwise be
initiated by the infrared radiation which
constitutes about 50% of the sun's spectral
energy. (fig. 1, h.)
 i) Incandescent Lamps

Incandescent lamps may, for specific

purposes, be used as light sources.
Since a considerable part of their
radiation is emitted in the infrared these
lamps may be put into action when visible
light as well as heat is required to effect a
photochemical reaction.
 j) Halogen Incandescent Lamps
Halogen lamps differ from ordinary
incandescent lamps in having a small
amount of I2 or Br2 added to the filling gas,
which is contained in a quartz bulb.
Such lamps are distinguished by:
their small dimensions, high efficiency ,
constant luminous flux and long lifetime.
These advantages are achieved by a
recycling process, by which the evaporated
tungsten is redeposited on the filament.
 k) Fluorescent Tubes
Various fluorescent tubes may be useful for
photochemical work in the visible and near UV
regions.
l) Vortex-Stabilized Plasma Lamps
These lamps have been produced by the
Giannini Scientific Corporation, Santa Ana, Falif.

Their spectrum varied by variation of filling gas,

gas pressure and current intensity.
.‫تنوع طيفها باختالف تعبئة الغاز وضغط الغاز وشدة التيار‬
 m) Low-pressure Gas Discharge
Lamps for the Far UV

Below 200 m quartz and oxygen begin to

absorb light appreciably.

For photochemical experiments in this

range the window material has to be:

lithium fluoride, calcium fluoride, sapphire,

and Oxygen have to be excluded.
 Besides the low-pressure mercury lamps
mentioned above with their weak emission
at 185 m, the following low-pressure
lamps (0.1-10 mm Hg) are useful:

Filling gas Important lines

Iodine 206 m
Xenon 130, 147 m
Krypton 116, 124 m
Hydrogen 122 m
n) Flash Lamps

In spite of the importance of flash

lamps in the studies of Fast Reactions
and in the elucidation of photochemical
mechanisms, these lamps have no
advantages in preparative organic
photochemistry.
 o) Lasers
 The laser light is monochromatic, parallel
and coherent
 Lasers offers the possibility of achieving
extremely high light intensities by focusing.

 Because of these properties lasers should

be kept in mind as a unique tool for solving
special problems.
More discussion on the use of lasers in
photochemistry will be found elsewhere.