Experimental set up for photochemical

reactions
Synthetic organic chemist (high intensity
light source, easy to handle, various
Flask size, specially designed systems)

Physical chemist or physical-organic

Chemist (mechanistic study)
 Basic equipments for photochemical reactions

Mercury vapor lamps (200-750 nm, 599 kj/mol-159 kj/mol)

1. Low pressure or resonance lamps (0.005-0.1 torr, operates at RT)

Emission at 253.7 and 184.9 nm

Hg (3P1) Hg (1S0) + h

Hg (1P1) Hg (1S0) + h

2. Medium pressure lamp (1-10 atm, and relatively high T)

Requires little time to warm up, more of direct irradiation lamp

3. High pressure lamp (200 atm and very high T)

Ideal lamp characteristic : Need of spectral overlap between the lamp and the absorption
spectrum of the compound to be irradiated.
 Lamps in conjugation with filters

Problems
# A greater degree of selectivity is required if irradiation into one of
the absorption bands of the molecule is required.
# Or if the product of the irradiation is sensitive to a wavelength different
from the one used to excite the starting molecule.

Solution
# Monochromatic source of light (Lamp and a diffraction grating)
# In conjugation with filters (solution or glass)
 Short and Long cutoff filter solutions

Wavelength of cutoff (nm) Chemical composition

Below 250 Na2WO4

Below 305 SnCl2 in HCl (0.1 M)

Below 330 2M Na3VO4

Below 355 BiCl3 in HCl

Below 400 KH phthalate + KNO2 (in glycol at

pH = 11)
Below 460 0.1 M K2CrO4 (NH4OH-NH4Cl at
pH = 10)
Above 360 1 M NiSO4 + 1M CuSO4 (in 5%
H2SO4)
Above 450 CoSO4 + CuSO4
Immersion Well Reactors
Components
# Lamps
# Immersion wells
# Reaction flasks
# Standard flasks
# Gas inlet flasks
# Flow-through flasks
# Larger capacity standard flasks
 Non-Rotating Annular
Photochemical Reactor

# Large Quartz immersion well.

# 400 watt medium pressure mercury lamp.
# Reactor base and carousel assembly
(non rotating), including support rod
and immersion well adjustable clamp.
# set of sample tube support rings for
eight 25mm sample tubes
# Only the inner or the outer tubes may be
irradiated effectively at one time
# UV Screen:- consisting of three black coated
consisting of three black coated aluminum
sections. A light tight lid, a removable front
and back section, that are joined by means
of a light tight seal
     
Semi-Micro Reactor
The semi-micro is a low cost, easy-to-use device for irradiating a standard
1 cm cuvette (or small tube) with either 254nm or 350nm radiation for any
preset time between 1 and 70 minutes. This reactor is ideal for preliminary
studies of small volumes of solution.
 # The multilamp reactors consist of a base, lid, six or
three lamp modules. Each module contains two
lamps.
# The base is hexagonal and provided with a centrally
located fan
# A number of modules up to six or three may be
operated.
# Switches are provided to control the fan and lamp
modules.
# Supports from the lid hold samples inside the
reactors. Magnetic strips are used to eliminate light
leaks between the lamp modules.

Multilamp Reactors: Six and Three Modules

Complete photochemical reactor comprising:

* Multilamp reactor base with cooling fan

and
control switches
* Three twin lamp modules
* Six lamps of customers choice
* Magnetic light sealing strips

One set of attachments for supporting the

reaction flask comprising :
* Reaction flask support base
* Flask support rod holder
* Support rod hinged lid
 Purity of solvent and gases

• Dilution (suppression of side reaction e.g.,

polymerization and dimerization.)
• Spectral transmission of solvent ( solvents
devoid of low-lying excited states are best)
• Purity of solvent (Oxygen free, impurities free)
 Transmission characteristics of various solvents

Solvent 10% Transmission (nm) 100% Transmission (nm)

Acetone 329 366
Acetonitrile 190 313
Benzene 280 366
Carbon Tetrachloride 265 313
Cyclohexane 205 254
Diethyl ether 215 313
Dimethyl sulfoxide 262 366
Ethanol 205 313
Hexane 195 254
Propan-2-ol 205 313
Tetrahydrofuran 233 366

Measured for a 1cm path length of pure solvent