Reaction between Hydrogen and Iodine ( Ø = 1)—

In this case the quantum yield is 1. In this reaction iodine molecule absorbs one quantum of energy
and dissociates into activated iodine atoms in the primary process.

1) I2 + hϑ → I* + I*

Secondary process is

2) I* + H2 → HI + H*

3) I* + H* → HI

Total reaction is I2 + H2 → 2H I

In secondary process, the activated iodine decomposes hydrogen gas and gives the
formation of activated hydrogen and HI. Finally one atom of activated iodine and one atom of
activated hydrogen collide and form HI.

This secondary reactions are without any side reaction, hence Ø = 1.

Reaction between Hydrogen and Bromine Ø < 1 —

In this reaction, bromine molecule absorbs one quantum of energy and gets dissociated into atoms.

1) Br2 + hv → 2Br

In secondary process—

2) Br + H2 → HBr + H (endothermic)

3) H + Br2 → HBr + Br (exothermic)

4) H + HBr → H2 + Br (deactivation)

5) Br + Br → Br2 (deactivation)

Second reaction is endothermic and third is exothermic reaction i.e. reaction (3) will proceed
much faster than that of 2nd. Therefore, the concentration of bromine atom will be much higher than
that of hydrogen atom formed in reaction (2). In above reactions formation of hydrogen gas and
bromine terminates the chain reaction. Thus although HBr is formed in reaction (2) and (3), the
reaction 4 and 5 dominates the overall reactions and affect the chain termination giving back
hydrogen and bromine. Thus without the chain propagation and loss of activity in the secondary
reactions the quantum yield is less than unity i.e. Ø = 0.01.

Reaction between H2 and Cl2 (Ø > 1)—

In reaction between H2 and Cl2—

In the primary process one quantum of energy is absorbed by chlorine molecule and gets
dissociated into atoms

1) Cl2 + hv → 2Cl
Secondary process—

2) Cl + H2 → HCl + H regen.

3) H + Cl2 → HCL + Cl regen.

Reaction 2 and 3 occur repeatedly and a chain reaction takes place . Ø = 1 x 10 5 to 106.

This chain continues till all H2 and Cl2 molecules are used up or till the chain reaction is broken by
any one of the following chain breaking or terminating reactions occurs—

4) Cl + Cl → Cl2

5) H + H → H2

6) H + Cl → HCl

7) Cl + wall → ½ Cl2

8) Cl + O2 → ClO2 (radical)

9) 2H + ½ O2 → H2O

In the presence of oxygen the chain may be terminated as reaction (8) and (9). The quantum
yield of the reaction is consequently lower in the presence of oxygen.

PHOTOSENSITIZATION ---

Some times the reacting molecules are unable to absorb the radiation itself. However if a
suitable atom or molecules (called sensitizer) is present to absorb the radiation, it can then pass the
absorbed radiation on the reacting molecules. Such a reaction is called as photosensitization
reaction.

The photosensitizers are the media which absorb the radiation energy and transfer to the
reacting system but they do not change themselves permanently.

1) Most important photosensitized reaction is the photolysis carried out in plants—

The green chlorophyll molecules acts as photosensitizer. They initiate reaction between CO2
and H2O to produce carbohydrates and oxygen as stable products.

6CO2 + 6H20 → C6H12O6 + 6O2

2) The dissociation of hydrogen—

The dissociation of hydrogen takes place in the presence of small amount of mercury
vapours, e.g. Reaction between carbon monoxide and hydrogen is sensitized by mercury vapours
which gives formaldehyde and glyoxal as final products.

Hg + hv → Hg*
 Hg* + H2 → 2H + Hg

H + CO → HCO

HCO + H2 → HCHO + H

2HCO → HCHO + CO

2HCO → CHO

CHO

Hydrogenation of ethylene, propylene, combination of hydrogen and nitrogen to form

ammonia, polymerization of ethylene are also mercury photosensitized reactions.

PHOTOCHEMICAL SMOG ----

Smog is nothing but fog that has become heavier and darker by smoke and chemical fumes.
It is mainly due to photochemical reactions. The main components of smoke are saturated
hydrocarbons, oxides of nitrogen and oxides of sulphur. Among these the concentration of NO in the
atmosphere is more in the morning due to fertilizer industries producing nitric oxide, ammonia and
urea. It slowly gets oxidized in presence of ozone to NO2. It is due to the photochemical reaction
between NO and O3

(1) NO + O3 → NO2 + O2

(2) NO2 + hv → NO2*

It dissociates to give chain carrying O atom

(3) NO2* → NO + O

This oxygen atom oxidizes the hydrocarbons in the polluted atmosphere resulting in the
formation of smog which includes formaldehyde, acrolein and peroxy acetyl nitrate (PAN). The PAN
can cause eye irritation, alteration in cardiopulmonary functions and can damage vegetation.

The possible reactions are –

(4) HC + O → HCO*
hydrocarbon free radical

(5) HCO* + O2 → HCO3

(6) HCO3 + NO → HCO2 + NO2

(7) HCO2 + NO → HCO + NO2

(8) HCO3 + NO2 → HCO3NO2 (PAN)

OZONE LAYER ---

The presence of ozone layer in stratosphere has a great significance. The ozone layer in the
stratosphere absorbs high energy i.e. uv radiations present in the sunlight. As a result about 90 to
95% of uv radiations are absorbed (of wavelength shorter than 300nm). In wavelength range 290 –
300 nm, the biological damage from solar radiation is very high. It causes sunburn (erythma) and it
damage DNA also. This creates serious problems for humans and for other life forms. Just decrease
in ozone concentration by 5% can produce millions of cases of skin cancer. It can also disturb the
energy balance of the earth, causing the general increase in temperature.

FORMATION OF OZONE LAYER ----

The earth is protected from extremely high energy uv radiations by oxygen in the atmosphere. The uv
radiations cleaves i.e. dissociates the oxygen molecule to form two free radicals

O2 (g) + h v (<240 nm) → O* (g) + O+ (g)

the oxygen atoms (free radical) attacks oxygen molecule to form ozone.

O+ (g) + O2 (g) + M → O3 + M

Where M = neutral body which carries excess of K.E. of oxygen atom to allow the
bond formation to make ozone.

Measurements have shown that large amount of uv radiations are present above earths
atmosphere but about 95 to 99 % of that is absorbed in ozone layer due to above reaction and
reactions taking place during decomposition of ozone.

O3 (g) + h v → O2 + O*
(220 to 320 nm)
The above reaction takes place by absorption of middle range uv radiations. The products of
the reaction can recombine to form ozone during which energy is given out in the form of thermal
energy.

DEPLETION OF OZONE LAYER----

Depletion of ozone layer occurs due to atmospheric pollution (1) like formation of NO or (2)
formation of halogenated derivatives of methane like CFCl 3, CF2Cl2, CF3Cl called as
chlorofluorocarbons i.e. CFCs.

The reactions are as follows—

(1) N2 (g) + 2O2 (g) → 2NO2 (g) + O2 (g)

NO (g) + O3 (g) → NO2 (g) + O2 (g)

NO2 (g) + O* (g) → NO + O2

therefore, Net reaction O3 + O* (g) → 2O2 (g)

 thus presence of nitric oxide brings about decomposition of ozone faster.

(2) CFCs are commonly used as refrigerant and aerosol propellants in spray. These are extremely
stable and long lived.

The photolysis of CFCs in the upper atmosphere and formation of chlorine atoms takes place
when they are exposed to uv radiation of about 200 nm.

CFCl3 (g) + h v → CFCl2* (g) + Cl* (g)

CF2Cl2 (g) + h v → CF2Cl* (g) + Cl* (g)

F3ClC (g) + h v → F3C* (g) + Cl*

The Cl* atom thus formed react with ozone and which slowly destroys the ozone layer in the
atmosphere.

Cl* (g) + O3 (g) → ClO + O2 (g)

ClO (g) + O* (g) → Cl* (g) + O2 (g)

Overall O3 (g) + O* (g) → 2O2 (g)

In the recent time the development of a hole has been observed in the ozone layer at the
pole mainly due to this reaction.

LUMINESCENCE---

When the electrons are excited by some means but not by high temperature or heat, it
produces light radiations. This phenomenon is known as luminescence.

Atoms by absorbing light radiations can get ionized or may produce electronic excitation.
This electronically excited atom has a life period of about 10 -7 to 10-8 sec. During this period if the
atom do not collide with another particle it re – emits part or all the energy absorbed and returns to
the ground state or intermediate state is known as Luminescence and the substances are known as
luminescent substances.

Luminescence is of three types—

1) Fluorescence, 2) Phosphorescence and 3) Chemiluminescence

1) FLUORESCENCE ---

WHEN an excited atom or molecule re – emits radiations back immediately and the emitted
radiations have a frequency less than that of the absorbed radiation, is called fluorescence. This
phenomenon is observed as long as source of light is present.

This phenomenon is observed as long as source of light is present.

It is observed in case of organic dyes like eosine, fluorescein, anthracene when dissolved in
benzene, vapours of sodium, mercury and iodine etc.

2) PHOSPHORESCENCE---

No sooner the light is removed the fluorescence disappears. In some cases even after the
removal of the source of light the emission of radiation continues, such phenomenon is termed as
‘phosphorescence’. A slow process of fluorescence can also be called as phosphorescence.

It can be observed during slow oxidation of phosphorous. Organic dyes when dissolved in
glycerine or fused boric acid and then cooled shows phosphorescence.

3) CHEMILUMINESCENCE---

It is reverse process of photochemical reaction.

The production of light radiation as a result of chemical reaction is known as chemiluminescence.

The light obtained is known as cold flame as there is no temperature involved.

e.g. –

1) slow oxidation of yellow phosphorus to phosphorous pentaoxide gives greenish glow.

2) Many Grignard reagents when oxidized by oxygen.

3) an oxidation of unsaturated silicon compounds.

4) Greenish cold glow produced by fire flies due to slow oxidation of amino acid (luciferin) present in
the insect.

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