Photochemical Kinetics

The rate laws which photochemical reactions follow are generally more complex than those for
thermal reactions.
Things to consider:

The rate of the primary activating process is controlled by the intensity of the activating
radiation used and is proportional to it.
The primary process is then followed by one or more reactions whose nature must be known
before a rate law for the over-all process can be deduced
To obtain information about all the possible changes that may occur, it is necessary to measure
the rates at which various reactants disappear, the rates at which products are formed and also
the effect of the intensity of light as well as its frequency on these.
From the data thus collected it is frequently possible to postulate a mechanism to account for
the observed facts. Of considerable help in this connection are atomic and molecular spectra of
the reactants involved.
For some reactions, these spectra allow the definite establishment of the nature of the primary
step.
In others, the process that cannot occur are eliminated and thereby the number of mechanisms
to be considered is reduced.

Example of an Hypothetical reaction

A2

2A

Mechanism:
(a)

A2 + hv

A*2 (activation)

k1

This is the absorption of a quantum of light by A2 with the formation of an activated molecule
(b)

A*2

2 A (dissociation)

k2

This activated molecule may undergo now dissociation

(c)

A*2 + A2

2 A2 (deactivation)

k3

Or this activated molecule may be deactivated by collision with an inactive molecule of A2

k1, k2 and k3 are the rate constants of these reactions.

The final product A is formed only in reaction (b). Consequently, the rate of formation A must be
given by
= k2CA*2
(11)
To eliminate from this rate of expression the unavailable concentration of active molecules, we
resort to the concept of stationary state. If we apply this concept to the intermediate A*2, we observe
that A*2 is formed by reaction (a) and that it disappears by reactions (b) and (c).

For reaction (a) the rate is determined only by the rate at which light is absorbed.
= k1Ia

(12)

The rate of disappearance of A*2 is given by the sum of the rates of reactions (b) and (c)
= k2CA*2 + k3CA*3CA*2

(13)

Formula for the condition of the stationary state

k1Ia = k2CA*2 + k3CA*2CA2
CA*2 =

(14)

Inserting CA*2 from equation (14) into equation (11), the rate of formation of A is seen to be
= k2CA*2 =

(15)

Finally, since for every two molecules of A formed one molecule of A2 reacts, the photochemical
efficiency of the process will be
=

= [

(16)

In photochemical rate equations time is generally expressed in seconds, concentrations either in

molecules or moles per cc. For the first of these concentration units Ia must be expressed in quanta of
light absorbed per cc per second, i.e., the total number of quanta absorbed in 1 second divided by the
volume of the absorbing medium. For the second concentration unit, on the other hand, Ia must be
taken in einsteins absorbed per cc per second, namely, the total number of einsteins aborbed in 1
second divided by the volume in cc.
Experimental Study of photochemical Reactions
To measure the rate of a photochemical reaction, it is necessary to irradiate a reaction mixture
with light of a selected wavelength and to observe the manner in which the concentration of reactants
or products varies with time.

The light sources used depend on the spectral range in which radiation is desired and include
filament lamps, carbon and metal arcs, various gas discharge tubes and lasers. The reaction cells may be
glass or quartz vessels, usually with optically plane windows for entrance and exit of light. In some
instances metal cells have been used with windows cemented to the ends. Glass can be used only in the
visible spectral range. Below 3500 A not only the cells but also any other optical parts through which the
light passes must be of quartz. With gases no provision need be made for stirring; solutions, however
must be agitated.
The radiant energy is measured with some form of thermopile, photomultiplier tube or
actinometer. The thermophile is essentially a multijunction thermocouple consisting usually of silver and
bismuth soldered to metal strips blackened with lamp, platinum or bismuth black. The radiation falling
on the blackened strips is absorbed almost completely and nonselectively, and is converted into heat.
The heat thus generated raises the temperature of the hot junctions above the cold and the current
generated thereby is measured. The current produced is proportional to the energy absorbed, and this
is, in turn, depends on the intensity of the incident light and the area exposed to it. Thermopiles are
calibrated with standard light sources.
Photocells and photomultiplier tubes may be used in place of thermopiles. Still other devices are
chemical actinometers, which are merely gas mixtures or solutions sensitive to light. When radiation
impinges upon these, a chemical reaction ensues whose extent is determined by the amount of energy
absorbed.
The rate of chemical reaction taking place in the system is ascertained in the usual manner. For
this purpose the change in some physical property can be followed, or samples can be removed
periodically from the cell and analysed. It is thus possible to collect data on the rate of the chemical
reaction and the light intensity, from which the rate law and the quantum yield may be deduced.
Photochemical Gas Reactions
The Photolysis of Ammonia
The photolysis or photochemical decomposition of ammonia was studied by Wiig, who found
that the reaction proceeds quantitatively according to

2NH3(g)
N2(g) + 3 H2
With an average quantum yield of 0.25 up to 500mm pressure of NH3. The following mechanism
has been proposed to explain these results:
(a) NH3 + hv
NH2 + H
(b) NH2 + H
NH3
(c) H + H
H2
(d) NH2 + NH2
N2H4
(e) N2H4 + H
NH3 + NH2
(f) NH2 + NH2
N2 + 2H2

The Combination of Hydrogen and Bromine

The photochemical combination of hydrogen and bromine was studied by Bodenstein and
Lutkemeyer between 160 and 218 degree Celsius. They found that any given temperature the rate of
formation of hydrogen is given by
[

(25)

And that the quantum yield , as given by,

=

(26)

The Hydrogen-Chlorine Reaction

In the photolysis of ammonia, the sequence of reactions leading to the final product is initiated
by formation of NH2 and H. Once formed, these particles are removed in every subsequent reaction, and
neither of these intermediates is generated except in the secondary step (e).

On the other hand, in the hydrogen-bromine reaction the cycle initiated by the appearance of
bromine atoms in reaction (a) is kept going by regeneration of these atoms in reactions (c) and (d), and
by formation of hydrogen atoms in (b). Every bromine or hydrogen atom thus formed is just capable of
starting a reaction as step (a) and hence each is able to start a new chain. Nevertheless the chains here
do not acquire great length because of their rapid termination and the quantum yield is thus low.

= kIaCH2

(27)

This rate equation can be accounted by the following mechanism:

(a) Cl2 + hv
2 Cl
k1
(b) Cl + H2
HCl + H
k2
(c) H + Cl2
HCl + Cl
k3
(d) Cl ( at walls )
Cl2
k4

Photosensitized Gas Reactions

When a reaction mixture is exposed to light to which the reactants are insensitive, no reaction
will take place. However, it is possible to introduce into the reaction mixture molecules or atoms which
will absorb the light, become excited, and then pass on this energy to one reactant and thereby activate
it for reaction. Substance acting in this manner is called a photosensitizer, while the reaction resulting is
said to be photosensitized.
Many mercury-photosensitized reactions have been investigated. These include decompositions
of H2, NH3, H2O, PH3, AsH3, various hydrocarbons, alcohols, ethers, acids and amines; hydrogenations
such as that of ethylene, propylene and butylene; combinations; such as that of oxygen and hydrogen to
water, oxygen to ozone, and hydrogen and nitrogen to ammonia ; and polymerizations, such as that of
ethylene. The dissociation of hydrogen is sensitized also by xenon, the polymerization of ethylene by
cadmium vapour. The latter is effective as well in the decomposition of ethane and propane into
hydrogen, methane and higher hydrocarbons. The halogens have also been employed frequently as
sensitizers. Thus chlorine, bromine and iodine sensitize the decomposition of ozone; bromine that of
Cl2O; while chlorine promotes the combination of oxygen and hydrogen to form water and of carbon
monoxide and oxygen to form carbon dioxide.

Photochemical Reactions in the Liquid Phase

Many substances undergo photochemical reaction when liquefied or dissolved in a solvent.
Again such reactions may be initiated by direct light absorption on the part of a reactant, or they may be
photosensitized, A priori it may be anticipated that the quantum efficiency of a photochemical process
will be less in liquid phase than for the same reaction in the gas phase. The reason for this is that in the
liquid phase an active molecule or atom may readily be deactivated by frequent collisions with other
active molecule, or by reaction with the solvent. Furthermore, because if the very short mean free path
in the liquid phase, free radicals or atoms when formed photochemically will tend to recombine before
they have a chance to get very far from each other. The net effect of these processes will be to keep the
quantum yield relatively low. In fact, only those reactions nay be expected to proceed to any extent for
which the primary products of the photochemical act are relatively stable particles. Otherwise the active
intermediates will tend to recombine or react with the solvent and thereby keep the yield low.