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# PROBLEM ON CHEMICAL KINETICS

QUESTION
You lead an interstellar expedition to a remote
planet, inhabited by aliens. Unfortunately, the
arrival of your spaceship initiates a reaction
causing the atmosphere to decompose by a
first-order rate law with a half-life of 13 hours.
Everyone will have to leave by the time when
only 13 % of the original atmosphere remains.
How much time do you have until then?

SOLUTION
k = ln 2 / t1/2
= ln 2 / 13
k = 0.053
1st order integrated rate equation is
A = A0 e-kt
0.13 A0 = A0 e-0.053t
0.13 = e-0.053t
ln 0.13 = -0.053 t
t = 38.5 hrs
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## Upper atmospheric (stratospheric) ozone protects us from

harmful ultraviolet radiation coming from the Sun. On the
other hand, ozone in the lower atmosphere (troposphere)
damages the human respiratory system as well as crops
and other plants, since ozone is a strong oxidizing agent.
Ozone formation in urban areas can be attributed mainly to
the two-step reaction mechanism:
NO2 + h NO + O k1 (1)
O + O2 O3

k2 (2)

## ( k1 includes the intensity of the solar radiation on an

average sunny day
Let us suppose that a small amount of NO2 is introduced
into the atmosphere and only reactions (1) and (2) take
place.
a) Which species is going to be in a quasi steadystate? Write down the algebraic equation to
calculate its concentration after an initial (so-called
induction) period.

## a) O atom is in quasi steady state as k 2 > k1

hence by SSA we have
d[O] / dt = k1[NO2] k2[O][O2] =0
which gives,
[O] = k1 [NO2] / k2[O2]
b) Differential rate equation
d[O3] / dt = k2[O][O2]
The integral form (i.e. the solution) is:
[O3] = k2[O][O2]t
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## The rate coefficient of reaction (1) is

0.0070 s1. The initial NO2
concentration is 2.5 x 1012 molecule
cm3.
c) What is the ozone
concentration after 1 minute?
d) What is the half-life of NO2?
e) What effect does temperature
have on the rate of ozone
formation? Why?
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## Substituting into the integral form for ozone

concentration the equation for O atom concentration
we get:
[O3] = k2 k1 [NO2][O2]t / k2 [O2]
= k1 [NO2]t
and NO2 decays in a first-order process:
[NO2]t = [NO2]0 exp(-k1t) = 2.48 x 1012 molecules/cm3
The oxygen atoms formed in the first reaction
practically all form ozone
[O3] = [NO2]0 [NO2]t = 0.02 x 1012 molecules /cm3
t1/2 = ln 2 / k1 = 99s
only small changes in the ozone concentration are
expected.
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## Ozone is not only formed but also

removed from the troposphere, mainly
by its reaction with NO:
NO + O3 NO2 + O2 k3 (3)
Assuming reactions (1-3), O3, NO and
NO2 will be in equilibrium.
k3 = 1.8 x 1014 cm3 molecule1 s1
f) What is the [NO]/[NO2] ratio, if
the equilibrium ozone
concentration is 9x1011 molecule
cm3?
8

## Equilibrium means no net production

or loss for any of the species:
d[NO2]/dt = -k1[NO2] + k3[NO][O3] =
0
K1 [NO2] = K3 [NO][O3]
[NO] / [NO2] = k1 / k3 [O3]
= 0.432
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## g) Assuming the same equilibrium

ozone concentration, how does
the above ratio change if we raise
the temperature from 10 C to 25
C? The activation energy of
reaction (3) is 10.8 kJ/mol?

10

## The ratio will decrease, since according to

the Arrhenius expression, k3 increases with
temperature.
k3 (T2) / k3 (T1)
= A exp [-EA / (R T2)] / A exp [-EA / (R T1)]
= exp [EA / R ( T-1 - T-2 )]
= 1.26
The concentration ratio has to be multiplied by
1/1.26 = 0.79, so the new value is 0.342.

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REFRENCE
icho2013.chem.msu.ru/.../Preparator
y_problems_IChO_2013...