Hydrogen-chlorine reaction

Cl2 + ℎ𝜈 → 2Cl
𝑘2
Cl + H2 → HCl + H
𝑘3 Steady state eqns:
H + Cl2 → HCl + Cl
𝑘4 d[Cl]/dt = 0 = 2Ia + ? ------------------ (1)
H + O2 → HO2 d[H]/dt = 0 = ? ------------------------- (2)
𝑘5
Cl + O2 → ClO2 From (2) calculate [Cl]. [Cl]=? ------------- (3)
𝑘6 Substituting (3) in (1), neglecting [O2]2, calculate [H].
Cl + X → ClX [H] = ? ---------------- (4)

X is any substance that removes Cl atoms

d[HCl]/dt=? ------------------ (5)
(5)-(2)=? ----------------------- (6)
4𝑘3
𝐼 [𝐻 ][𝐶𝑙2 ]
𝑘4 𝑎 2
At low [O2], d[HCl]/dt = 2k3[H][Cl2] = 𝑘 𝑘 𝑘 𝑘 𝑘
3 6 𝐶𝑙2 𝑋 + 𝑂2 { 𝐻2 + 3 5 𝐶𝑙2 + 6 𝑋 }
𝑘2 𝑘4 𝑘2 𝑘4 𝑘2
𝑑 𝐻𝐶𝑙
𝜙 = 𝑑𝑡 =? (from Eq. 4)
𝐼𝑎
 Beer-Lambert Law

Attenuation of a light beam passing through an absorber.

I → intensity of the beam is the number of quanta of light passing through unit area of a
plane perpendicular to the direction of the beam in unit time.
-dI → number of quanta absorbed in the distance, dx. The probability of absorption in the
distance, dx, is – dI/I ; if the slice is thin, the probability of absorption is proportional to
the thickness of the slice and the number of absorbing molecules in the slice, that is, to
the concentration of the absorbing species.
If there are several kinds of molecules present, each with a different ability to absorb light
of the frequency in question, then

The constants, 𝑘1 , 𝑘2 , . . . , are characteristic of the substances in question. For

any substance the value of k depends on the wavelength.

Integrated form: Or
 The absorbance, A, is defined by:

For mixtures of independently absorbing substances the absorbance is given by

where c1 , 𝑐2 , . . . are the concentrations of the substances having molar absorption

coefficients of 𝜖1 , 𝜖2 , . . . .
 Recall: 𝐴 = − log 𝑇; 𝑇 = 𝐼/𝐼0

=A
Note: cell length is just
a parameter = 1cm (say)
 Ozone layer in atmosphere

Formation of O3 in the stratosphere is an example of photochemical stationary

state. State that do not change with time, e.g. [O3]

Simplified mechanism for the formation and destruction of ozone in stratosphere --

also accounts for ‘oxygen-only’ atmosphere:

Very slow and can be neglected.

M is an arbitrary third body, such as O2 in an ‘oxygen-only’ atmosphere, which helps to

remove excess energy from the products of combination and recombination reactions.

Exothermic reactions and result in heating of atmosphere.

Protective role of Ozone!

 Kinetics of Ozone formation

J’s are photodissociation constants –

probability of dissociation of a molecule
per second by light absorption.
Unit is s-1 (like 1st order rate constant).

If the absorption of solar radiation in the first and third steps is steady, the concentration
of ozone rises to a steady level

-------- (i)

Since [O] is very low, d[O]/dt is assumed to be zero at steady state.

-------- (ii)
Adding eqs. (i) and (ii)

-------- (iii)

From experimental observation it is known that:

So from Eq. (ii) -------- (iv)

Substituting for [O] from Eq. (iv) in Eq. (iii) we have:

-------- (v)
 Obtained by taking
d[O3]/dt=0 in Eq. (v)

The above model (Chapman) overestimates the concentration of ozone in the

stratosphere because other trace species X contribute to catalytic
enhancement of the termination step O3 + O → 2O2 according to
 Chlorofluorocarbons (CFCs)
CFCs (Freons) are very harmful due to reactive nature of Cl radical and propagate
chain reaction. One Cl radical react with up to 104 O3 molecules.

Cl atoms are formed from the photolysis of CFCs (chlorofluoro carbons)

CFCl3 + h𝜈 → CFCl2 +Cl

At the level of Ozone layer
CF2Cl2 + h𝜈 → CF2Cl +Cl

UV radiation

Cl atoms act as catalyst in the

decomposition of Ozone layer

Chlorofluorocarbons are being phased out according to international agreements

and alternatives, such as the hydrochlorofluorocarbons (HCFCs) and
hydrofluorocarbons (HFCs) for e.g. CH2FCH3, are being used.
 Hydrochlorofluorocarbons (HCFCs)

HCFCs deplete less stratospheric ozone than equivalent amount of CFCs because:

i. HCFCs have shorter lifetimes than CFCs (less reactive Cl in stratosphere).

ii. HCFCs contain C-H bond. H is attached by OH radical in the lower part of
atmosphere (Troposphere) and Cl is released (oxidised). Cl typically combines with
other chemicals to form compounds that dissolve in water and ice and are
removed by precipitation. So Cl doesn’t reach the stratosphere.

iii. Photolysis rates of HCFCs are slower than CFCs in stratosphere. So less Cl is
released from them in lower stratosphere than CFCs.

iv. HCFCs are degraded significantly by two mechanisms in the atmosphere as

opposed to CFCs.
 Hydrofluorocarbons (HFCs)

HCFCs still contain Cl, it has a potential for ozone depletion, hence 2nd generation
alternatives HFCs are introduced with zero ozone depletion potential.

CF3 radicals produced from its decomposition are shown to be insignificant.

Some HFCs have adverse environmental effects.

Some decompose in atmosphere to produce trifluoroacetic acids which is

harmful to some bio-species.
 Photosynthesis
In photosynthesis CO2 and H2O are converted to the glucose moiety as starch.
The overall process can be represented by
Visible light

where (CH2O) represents one-sixth of a glucose moiety. [(CH2O)n is

the general formula for carbohydrate].

• Photosynthesis is carried out by plants, algae, and certain kinds of bacteria

that have chloroplasts. The chloroplasts contain chlorophyll a, chlorophyll b,
carotenes, electron carriers, and enzymes, and they have internal membranes
that keep reactants separated.

• The first step in photosynthesis is the absorption of light by a chlorophyll

molecule. Chlorophylls a and b contain networks of alternating single and double
bonds and have strong absorption bands (one between 600-680nm and other
between 380-480nm) in the visible part of the spectrum, with molar absorbancy
indices greater than 105 L mol−1 cm −1.
• The energy of the absorbed photon is transferred from one chlorophyll molecule to
another until it reaches a site called a reaction center. Experiments show that about
eight photons of visible light have to be absorbed per O2 liberated.