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Original Title: Varied Problems on Chemical Kinetics

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You are on page 1of 13

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

3

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)

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.

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

5

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?

6

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.

7

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

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

9

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 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.

11

REFRENCE

icho2013.chem.msu.ru/.../Preparator

y_problems_IChO_2013...

www.answers.yahoo.com

www.bioinfoamss.org/.../steady_state

_laws_in_enzyme_kinetics.

www.wikipedia.org/wiki/Steady_State

_theory

12

THANK

YOU

13

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