You are on page 1of 8

159

Reaction kinetics

The investigation of the factors that affect the rate of a chemical reaction is important
in the study of physical chemistry. The temperature and the addition of a catalyst can
both affect the progression of a chemical reaction.

a explain and use the term rate of reaction

b explain qualitatively, in terms of collisions, the effect of concentration 



changes on the rate of a reaction

c explain and use the term activation energy, including reference to the Boltzmann
distribution

d explain qualitatively, in terms both of the Boltzmann distribution and of collision


frequency, the effect of temperature change on the rate of a reaction

REACTION KINETICS

CEDAR COLLEGE REACTION KINETICS


160
Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

8 Reaction kinetics
The investigation of the factors that affect the rate of a chemical reaction is important in the study of
physical chemistry. The temperature and the addition of a catalyst can both affect the progression of a
chemical reaction.

Learning outcomes
Candidates should be able to:

8.1 Simple rate a) explain and use the term rate of reaction
equations; orders
b) explain qualitatively, in terms of collisions, the effect of concentration
of reaction; rate
changes on the rate of a reaction
constants
c) explain and use the terms rate equation, order of reaction, rate
constant, half-life of a reaction, rate-determining step
d) construct and use rate equations of the form rate = k[A]m[B]n (for
which m and n are 0, 1 or 2), including:
(i) deducing the order of a reaction, or the rate equation for a
reaction, from concentration-time graphs or from experimental
data relating to the initial rates method and half-life method
(ii) interpreting experimental data in graphical form, including
concentration-time and rate-concentration graphs
(iii) calculating an initial rate using concentration data
(integrated forms of rate equations are not required)
e) (i) show understanding that the half-life of a first-order reaction is
independent of concentration
(ii) use the half-life of a first-order reaction in calculations
f) calculate the numerical value of a rate constant, for example by
using the initial rates or half-life method
g) for a multi-step reaction:
(i) suggest a reaction mechanism that is consistent with the rate
equation and the equation for the overall reaction
(ii) predict the order that would result from a given reaction
mechanism (and vice versa)
h) devise a suitable experimental technique for studying the rate of a
reaction, from given information

8.2 Effect of a) explain and use the term activation energy, including reference to the
temperature on Boltzmann distribution
reaction rates and b) explain qualitatively, in terms both of the Boltzmann distribution and of
rate constants; the collision frequency, the effect of temperature change on the rate of a
concept of activation reaction
energy
c) explain qualitatively the effect of temperature change on a rate
constant and hence the rate of a reaction

CEDAR COLLEGE REACTION KINETICS

Back to contents page www.cie.org.uk/alevel 27


161

REACTION KINETICS

BOLTZMANN DISTRIBUTION OF MOLECULAR ENERGY

All particles have energy - the


greater their temperature, the more
NUMBER OF MOLECUES WITH

energy they possess. The greater


A PARTICULAR ENERGY

their kinetic energy the faster they


travel.

Because of the many collisions


taking place between molecules,
there is a spread of molecular
energies and velocities.

MOLECULAR ENERGY
2

CEDAR COLLEGE REACTION KINETICS


162

BOLTZMANN DISTRIBUTION OF MOLECULAR ENERGY

No particles have zero energy/velocity


NUMBER OF MOLECUES WITH
A PARTICULAR ENERGY

Some have very low and some have


very high energies/velocities

Most have intermediate velocities.

MOLECULAR ENERGY
3

INCREASING TEMPERATURE
Shift to higher energies/velocities
TEMPERATURE
T2 > T1 Curve gets broader and flatter due to the
NUMBER OF MOLECUES WITH

greater spread of values


A PARTICULAR ENERGY

T1
Area under the curve stays constant - it
corresponds to the total number of particles

T2

CEDAR COLLEGE REACTION KINETICS


163

DECREASING TEMPERATURE

T3 TEMPERATURE Shift to lower energies/velocities


T1 > T3
NUMBER OF MOLECUES WITH
A PARTICULAR ENERGY

Curve gets narrower and more pointed


T1 due to the smaller spread of values

Area under the curve stays constant - it


corresponds to the total number of
particles

MOLECULAR ENERGY
5

REVIEW
No particles have zero energy/velocity
TEMPERATURE
T3 Some particles have very low and some
T2 > T1 > T3
NUMBER OF MOLECUES WITH

have very high energies/velocities


A PARTICULAR ENERGY

T1
Most have intermediate velocities

As the temperature increases the


T2 curves flatten, broaden and shift to
higher energies

MOLECULAR ENERGY
6

CEDAR COLLEGE REACTION KINETICS


Figure 9.8 The Boltzmann distribution of molecular energies, showing
the activation energy.
164 Check-up
3 a Wha
In Figure 9.8, the activation energy is labelled. b Exp
Remember that the activation energy is the minimum can
ACTIVATION ENERGY
energy required for particles to react. When we raise the - E A

temperature of a reaction mixture, the average kinetic 10 °C risereac in


(movement) energy of theThe particles
shaded areaincreases.
shows theParticles as does the ra
Number of molecules

in solution and in gases will proportion of molecules in


move around more quickly Therefore i
the sample that have enough
at a higher temperature, resulting in more
energy to cause frequent
a chemical
of reaction be
collisions. However, experiments change when show they us that the effect
collide. Factincrease
• the file
of temperature on rate of reaction cannot be totally Ludwigquick
more Boltzm
Ea
peersproport
• the in his lif
explained by more frequent collisions. The key factor
0 to feel disillus
result in a r
is that
0 the proportion of successful
Ea – at and above this energy
collisions increases
Molecular energy
himself. Soon
greatly as we increase the temperature.
the molecules have enough The distribution particles exc
by the scientifi
of molecular energiesenergy tochanges as we raise the temperature,
collide effectively. is the more
as shown in Figure 9.9. The curve flattens and the peak
7

Figure
shifts9.8to The
theBoltzmann
right. distribution of molecular energies, showing
the activation
The areaenergy.
under the curve represents the number of 9.4 Cata
Check-u
particles. The shaded area shows the number of particles In Figure 9.6 w
with energy greater than the activation energy. For a 3 a Whm
an alternative
In Figure 9.8, the activation energy is labelled. Ex
b ener
activation
Remember that the activation energy is the minimum
distributioncan (F
energy required for particlesTEMPERATURE
INCREASING to react. When we raise the rea
temperature of a reaction mixture, the average
When the sample is heated, the mean energy of the
kinetic
(movement) energy
molecules of the
increases. Thereparticles
is a wider increases.
spread of values.Particles
in solution and in gases will move around more quickly
Number of molecules

at a higher temperature, resulting A greater


in proportion
more of
frequent
Number of molecules

T °C
collisions. However, experiments Ea
molecules than before exceed
show us
the activation thatsothe effect
energy,
Fact file
of temperature on rate of reaction increasing rate ofbe
cannot reaction.
totally Ludwig Boltz
peers Molecul
in his
explained by (T+10)°C
more frequent collisions. The key factor these lo
to feelcannot
disillur
is that
0 the proportion of successful collisions increases
0 Molecular energy himself. Soo
greatly as we Ethe a – at and above
increase the this energy
temperature. Th e distribution 0
molecules have enough by
0 the scient
of molecularenergy energies changes
to collide as we raise the temperature,
effectively.
as shown in Figure 9.9. The curve flattens and the peak
8

Figure 9.9 The Boltzmann distribution of molecular energies at Figure 9.10 The B
shifts to the right.
9.4 Cata
temperatures T °C and (T + 10) °C, showing the activation energy. the activation ener
The area under the curve represents the number of
particles. The shaded area shows the number of particles In Figure 9.6
CEDAR COLLEGE REACTION KINETICS
with energy greater than the activation energy. For a an alternative
articles In Figure 9.6 we saw how a catalyst works by providing
ra an alternative mechanism (or165route) with a lower
activation energy. We can show this on a Boltzmann
distribution (Figure 9.10).
CATALYSTS
Number of molecules

ed
Coloured areas indicate the proportion
of molecules whose energy exceeds
Molecules with the activation energies Ea(cat) and Ea.
these low energies
cannot react.
r energy
0
0 Ea(cat) Ea Molecular energy
9

t Figure 9.10 The Boltzmann distribution of molecular energies, showing


y. the activation energy with and without a catalyst.

9 Rates of reaction 157

CATALYSIS
Catalysts increase the rate of a chemical reaction. They do this by providing an
alternative pathway for the reaction with lower activation energy.

We can divide catalysts into two main classes.

Catalysis

Homogeneous Catalysis Heterogeneous Catalysis


Occurs when the catalyst is in the Occurs when the catalyst is in a different phase
same phase as the reaction mixture. to the reaction mixture. For example,
For example: hydrogen ions catalyse decomposition of aqueous hydrogen peroxide
the hydrolysis of esters. catalysed by manganese(IV) oxide.

10

CEDAR COLLEGE REACTION KINETICS


166

HOMOGENEOUS CATALYSIS
Homogeneous catalysis often involves changes in oxidation number of the ions involved
in catalysis.

Ions of transition elements are often good catalysts because of their ability to change
oxidation number.

Examples:

1. The catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric


sulfur dioxide.

2. Catalytic role of Fe3+ in the I–/S2O82– reaction.

11

HETEROGENEOUS CATALYSIS
The mechanism of this catalysis can be explained using the theory of adsorption. Chemical
adsorption (also called chemisorption) occurs when molecules become bonded to atoms on
the surface of a solid.

You must be careful to distinguish between the words adsorb and absorb. Adsorb means to
bond to the surface of a substance. Absorb means to move right into the substance – rather
like a sponge absorbs water.

Examples:

1. Iron in the Haber Process

2. Transition elements in catalytic converters

3. Vanadium (V) oxide in the contact process

12

CEDAR COLLEGE REACTION KINETICS