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
 2. Light Filters
The use of Monochromatic light or of a
selected portion of the spectrum is often
necessitated in preparative photochemistry
in order to prevent primary photoproducts
from undergoing secondary photoreactions.

Conventional Prism or Grating

monochromator systems cannot provide
monochromatic beams of sufficiently high
intensity.
Several types of Glass and liquid filters,
may be used in combination with the light
sources, to serve the purpose of selecting
narrow lines or portions of the spectrum.

In most cases combination of several filters

is necessary.

Two types of filters may be distinguished :

 Cut-off filters & Band-pass filters

Cut-off filters:

In electronics, cut-off frequency or corner frequency is

the frequency either above or below which the power
output of a circuit, such as a line, amplifier, or electronic
filter has fallen to a given proportion of the power in the
passband.
 Band-pass filters
A band-pass filter admits frequencies within a given
band, rejecting frequencies below it and above it
When using filters, it must be kept in mind that
filters heat up when absorbing light and may
change their spectral properties, or they may be
damaged otherwise by heat or by light.

For this reason, most filters must be

preirradiated and checked spectroscopically.
 a) Solid filter materials
Solid filters are most useful for preparative work
with the immersion-type photoreactor.
The walls of the immersion well normally act as
such filters.

Their spectral properties depend on the type of

material employed and also band-pass filter glass
may be used for lamp housings.
 Table 1
No. material thickness
1 Lithium fluoride (a: fresh; b: aged) 1-2 mm
2 Suprasil 10 mm
3 Sapphire 1mm
4 Fused quartz 10 mm
5 Corning 9863 glass 3 mm
6 Solidex 2 mm
7 Pyrex clear chemical glass 2 mm
8 Coming 5850 glass 4 mm
9 Coming 5970 glass 5 mm
10 Window glass 2 mm
11 Wertheimer Filterglass GWCa 2 mm
12 Wertheimer Filterglass GWV 2 mm
 For Knowledge

Immersion wells made from

Vycor 7910, Corex 9700 and Pyrex
7740 are now available for lamps
from 100 Watts onwards from
Hanovia.
 b) Liquid filters
A great variety of liquid filter systems have been
described in the literature.

When used in immersion-type photoreactors,

these liquid filters will either be contained in a
separate filter jacket of the onion-type reactor or
may serve as coolant proper for the immersion
lamp.
 Table 2
No. Solute [g/liter]
NaBr.2H2O CaCl2 Pb(NO3)2 Hg(NO3)2 Ag2SO4
1 500 0.05
2 400 0.024
3 400 0.16
4 400 1.20
5 500 6.40
6 80 375 0.050 0.10 0.30
7 400 0.065 0.10 0.39
8 400 1.00
9 650 3.00
 c) Interference Filters
When using directed light, very pure and intense
monochromatic radiation can be obtained by means of
interference filters. There are two types of interference
filters:
Wide band filters & Line filters
Which differ from each other in the half-peak width.
Compared with color glass filters and other absorption
type filters the interference filters have the advantage
of reflecting the undesired spectral portion so that they
are not overheated so easily.
 For Knowledge
When mounting the interference filter attention
must be given to the mirror face positioned
towards the light source.

In combination with, for example, a 2000 W

xenon projector a good selection of spectral
bands in the visible region can be attained
by means of the interference filters filtraflex
K 1-7 of Balzers (Fig. 4).
 d) Reflection Interference Filters
With usual interference filters lines or bands
in the wavelength region below 320 m can be
singled out only with difficulty.
In these cases, the newly developed
reflection interference filters UV-R for
wavelengths 250, 280, and 310 m (Schott)
may be successfully employed.
 Solar Energy
The Sun is a star, 150 million km away from the
earth and 1.33 million times as the size of the earth.
Sunlight takes 8.33 mins. to reach earth.

Origin:
Solar energy is a result of the fusion of H2 to He.
655 million tons of H2 is converted to 650 million
a ton of He every second.
The 5 million tons loss in mass is converted to
energy.
 A very small part of this emitted
solar energy reaches earth.

21H 2
1 2 4He + Solar Energy

655 MT/S 650 MT/ S ≡ 5MT/S (E)

 Uses of solar Energy:
1- Heating of water by solar heaters.

2- Solar furnaces are used in melting

metals and in cooking.

3- Desalination of water.
4- The generation of electricity using
steam turbines (steam is resulting from
boiling water by solar energy ).

5- The generation of electricity using solar

cells of different kinds where light is
used to develop a potential difference.
 Solar Energy Storing:

(1) Storing of Solar Energy in Organic Compounds:

Storing of solar Energy is plants [Photosynthesis]:

The living plant contains a green material

which is chlorophyll inside the green
plastides, this absorbs solar energy and
converts it into chemical energy.
 Steps of storing solar energy:

Light energy
6 CO 2 + 6 H 2O C 6 H 12O 6 + 6 O2
Chlorophyll

Chlorophyll absorbs light, activated and

convert it through a series of chemical reaction
into chemical energy in the form of special
molecules containing H2 and O2:
• Water is decomposed into H2 and O2.

• The green plastids keep hydrogen for

some time, and O2 evolved as gas.

• The hydrogen inside the plastids

reduces CO2 through successive steps
until it is converted to sugar
The use of energy stored in sugar
Molecules
a) In Nutrition:
Sugar molecules is converted into more
complicated molecules like sucrose,
cellulose. Fats & Proteins used as food for
humans, animals as well as plants.

b) As Fuel:
Trees and herbs are used as fuel by man after
drying, as charcoal.
 (2) Storage of Solar Energy in
Inorganic Compounds
Solar energy can be stored during the day to be
used during the night for heating small houses &
greenhouses via thermochemical reactions,

a) Hydrated sodium sulfate:

 b) Dilution of Conc. H2SO4:

Solar Energy
H2SO4 (dil) H2SO4 (conc) + H 2O
Day time
Exothermic
H2SO4 (conc) + H2O H2SO4 (dil) + Heat
(Night)

c) Slaking quicklime:

Quicklime is CaO that reacts with water

to form slaked lime (Calcium hydroxide).
 Night
CaO + H 2O Ca (OH)2 + Heat

Ca(OH)2 Solar Energy Ca O + H 2O

 The Different Ranges of Light

What is Light:

Light is just one portion of the various

electromagnetic waves flying
through space.
 Visible Microwaves
X- Ray Light

I. R
U.V 380-770 nm
770- 1,000,000

The electromagnetic spectrum covers

an extremely broad range from
radiowaves with  of a meter or more,
down to x-rays with wavelengths of less
than billionth of a meter.
 Optical radiation lies between radio
waves and x-rays in the spectrum, exhibiting
a unique mix of ray wave and quantum
properties.

 At x-ray and sorter wavelengths,

electromagnetic radiation tends to be
particle-like in its behavior, whereas toward
the long wavelength the behavior is mostly
wavelike.
The visible portion occupies an
intermediate position, exhibiting both wave
and particle properties in varying degrees.

Like all electromagnetic waves, light

waves can interfere with each other,
become directionally polarized, and bend
slightly when passing an edge.

These properties allow light to be filtered

by wavelength filters or amplified
coherently as in a laser.
 Ultraviolet light:

Short wavelength UV light exhibits

more quantum properties than its
visible and I.R. counterparts.

U.V. is arbitrary broken down into

three bands according to its effects :
 least energy -Least harmful -
- most commonly found type
UV-A : of U.V. - often called Black
(315-400) U.V. - used for its relatively
nm harmlessness and its ability
to cause fluorescent
materials to emit visible light
- appearing glow in the dark.
 The more destructive form of U.V.
It has enough energy to damage
biological tissues, and cause skin
cancer.
UV-B: Since most U.V.B. light is blocked
by the atmosphere, a small change
(280-315)
in the ozone layer could dramatically
nm increase the danger of skin cancer
h
O3 O2 + O
h
2 O3 3O 2
 Almost completely absorbed in the
air within a few hundred meters.
When photons collide with O2, the
UV-C : energy exchange forms O3.
(100-280) UV-C was never observed in
nature.
Germicidal UV-C lamps are even
used to purify air and water, due to
their ability to kill bacteria.
Atmosphere Layers:
Exosphere > 700km - Thermosphere 80-700 km
Mesosphere 50-80 km - Stratosphere 12- 50 km
Troposphere 0 -12 km

Other secondary layers are distinguished

within the 5 principle layers ( e.g. Ozone
layer, ionosphere, Homo &
heterospheres….).
Ozone layer:
~90% of the O3 is contained within the
stratosphere layer.
- The O3 concentration in this layer is 2-8 ppm
which is much higher than in the lower
atmosphere but still very small compared to the
main components of the atmosphere.

- It is mainly located in the lower portion of the

stratosphere though the thickness varies
seasonally and geographically.
 The Fate of Excited Molecules
Physical Processes: (Jablonski Diagram):
• When a molecule has been
photochemically promoted to an excited
state, it does not remain for long.
Most promotions are from SoS1.

• Promotions to S2 or S3 etc.. takes place

but usually drops very rapidly to S1 state
(~10-11 - 10-13 Sec.), by collisions with
neighboring molecules (energy cascade).
• Similarly, the initial excitation and the
decay from higher singlet states initially
populates many of the vibrational levels of
S1, but these also cascade, down to the
lowest vibrational levels of S1. Therefore,
it’s in most cases the only important exited
singlet state.

• This state (lowest vibrational level of S1)

could undergo various physical or
chemical processes as shown in a
modified Jablonski diagram as follows:
Figure 4: Modified Jablonski diagram showing transitions
between exited states and the ground state Radiative processes
are shown by straight lines radiationless processes by wavy
lines, IC = internal conversion, ISC = intersystem crossing,
VC = vibrational cascade, hνf = fluorescence,
hνP = phosphorescence.
back
Jablonski Diagram
1. Absorption.
2. Fluorescence.

3. Phosphorescence.
4. Vibrational relaxation.

5. Intersystem crossing.
6. Internal conversion.
 Very Important
Table 4: Physical processes undergone by excited molecules.
Excited states higher than S1 or T, are omitted.

S0 + hS1
Excitation (Absorption)
Vibrational relaxation
S1u S1 + heat
Fluorescence
S1 S0 + h Internal conversion
S1 S0 + heat Intersystem crossing
Vibrational relaxation
S1 T1u
Phosphorescence
T1u T1 + heat
Intersystem crossing
T1 S0 + h

TSheat
Singlet-singlet
 Transfer (photosensitization)
S1 + A (S0) S0 + A (S1)

T1 + A (S0) S0 + A (T1) Triplet-triplet transfer

(photosensitization)
 1 – Internal conversion (ic)

- A molecule in the S1 state can cascade

through the vibrational levels of So and thus
returns to the GS by giving up the energy in
small increments to the environment, it is a
quite slow process because the amount of
energy is large, (nonradiative transitions
represented by wavy arrows).
- Because it is slow, most molecules in S1
adopt other pathways.
 2- Vibrational Cascade,
vc,
(Vibrational Relaxation)

It is a nonradiational process.
This pathway is resulting from transitions
from higher vibration levels to the lowest
vibrational level (Vo) of the state.
 3 – Intersystem crossing (isc)
- Most molecules in S1 can undergo isc to the
lowest triplet state T1. An important example
is a benzophenone (100% of S1T1).

- ISC is of course a forbidden pathway since

the angular momentum problem must be
taken care of, but this often takes place by
compensations elsewhere in the system.
- ISC is a nonradiative transition represented
by wavy arrows.
 4– Fluorescence (f)
- A molecule in the S1 state can drop to low
vibrational levels of So all at once by giving
off the energy in the form of light.
- It takes 10-9 sec (relatively slow !!)
S1So (fluorescence) & S2So is possible.

- Because of the possibility of fluorescence,

any chemical reactions of the S1 must take
place very fast, or fluorescence will occur
before they can happen.
 5 – Phosphorescence:
A molecule in T1 may return to the So by
giving up the heat (isc) or light. Of course,
the angular momentum difficulty exists
here, so isc and phosphorescence are
very slow (10-3 to 10-1 sec). i.e., T1 states
have a longer lifetime than S1.
6- Luminescence:
Under circumstances where the spin
multiplicity (s or t) of the emitting state
( phosphorescence or fluorescence) is in
doubt due to the mixing of excited
electronic states ( as sometimes happens
in inorganic molecules containing heavy
transition elements), the emission is
referred to as “Luminescence”.
 7- Slow fluorescence:
• It is the third type of emission. It has the
same  as fluorescence but occurs much
more slowly.

• It is caused when a molecule in T1 acquires

thermal energy to raise it to a higher
vibrational level equal in energy to the
lowest S1 level and then crosses to So
 Slow
1 S1 S0
SC Fluo

• Slow fluorescence can also be caused by

collision between two triplet molecules in
which an excited singlet is produced.
 8 – Photosensitization:

* A molecule in the excited state (S1 or

T1), if nothing happens to it first, may
transfer its excess energy all at once to
another molecule in the environment.

* i.e. transfer of excess energy of excited

molecule all at once to another one
D* + A → D + A* Donor - Acceptor

D*T1 + ASo →DSo + A+T1 Triplet- Triplet Transfer

 D*S1 + ASo →DSo + A*S1 Singlet- Singlet Transfer