CHM 271

CHEMICAL KINETICS
CHAPTER 5

5.1 Rates of reaction

5.2 Factors affecting rates of reaction
5.3 Rate Law and Order of reaction
5.4 Methods to determine order of reactions
5.5 Relation between rate and temperature
5.6 Reaction mechanism
5.7 Catalytic kinetics

Mdm Nurul Amni Abdullah 1

Faculty of Applied Sciences
amni2468@uitm.edu.my
• 5.1 Rates of reaction
LESSON OUTLINES
• 5.1.1 Definition and units
• 5.1.2 Determination of rates of reaction

• 5.2 Factors affecting rates of reaction

• 5.2.1 Collision theory

• 5.3 Rate law and order of reaction

• 5.3.1 Rate law for zero, first and second order of reactions

• 5.4 Methods to determine order of reactions

• 5.4.1 Initial rate
• 5.4.2 Integrated rate law
• 5.4.3 Half Life

• 5.5 Relationship between rate and temperature

• 5.5.1 Arrhenius equation
• 5.5.2 Determination of activation energy using Arrhenius equation by graphical method and
calculation

• 5.6 Reaction mechanism

• 5.6.1 Definition: reaction mechanism, elementary steps, molecularity, rate-determining step
• 5.6.2 Relationship between rate law and reaction mechanism
• 5.6.2.1 A mechanism with a slow step followed by fast step
• 5.6.2.2 A mechanism with a fast-reversible step followed by a slow step

• 5.7 Catalytic kinetics 2

• 5.7.1 Homogeneous and heterogeneous catalysis
• 5.7.2 Enzyme catalysis
 LESSON OUTCOMES

At the end of this lesson, the students should be able to:

• Define and determine the rate of reaction

• Explain the factors affecting rate of reaction
• Determine the rate law and order of reaction
• Apply Arrhenius equation for calculation of activation energy (Ea)
• Relate between rate of reaction and temperature
• Predict the rate law from reaction mechanisms
• Describe the two types of catalyst and catalysis

3
Chemical Kinetics or Reaction Kinetics

The study of the rate of chemical reactions

Basically….How fast does a

chemical reaction occur? 4
 5.1 RATE OF REACTION
• A measure of the change in the concentration of a reactant or
product in a given time.

[ x]
rate =
t
Unit = concentration
time
= mole / liter or mol dm-3
second second
= mol L-1 s-1 5

= M s -1
• During a chemical reaction, the reactants are consumed while
the products are formed.
• When the reactants transform to products;
• The concentration of reactants decreases with time.
• The concentration of products increases with time.

SHORTER TIME REACTION – HIGHER RATE

LONGER TIME REACTION – LOWER RATE

1
Rate α
time
6
 For a chemical reaction A → B,
A (REACTANT) → B (PRODUCT)
The rate of reaction is
• The decrease in reactant concentration , [A] per
unit time
• The increase of product concentration, [B] per unit
time
7
 A B

time

[A]
rate = -
t

[B]
rate =
t
8
Consider a general reaction :

Reactant (r) → Product (p)

From the tangent to the curve we can write the rate of

disappearance (or consumption) of reactant r as
[r ] d [r ]
rate = - =-
t dt
the minus sign indicates that the
concentration of r decreasing with time.

and the rate appearance (or formation) of product p as

[ p] d [ p]
rate = = 9

t dt
 Let’s consider the rates for chemical reaction

NO(g) + ½ O2 (g) → NO2(g)

Rate of disappearance of NO =

Rate of disappearance of O2 =

Rate of appearance of NO2 =

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 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent
slope of
tangent

[Br2] [Br2]final – [Br2]initial

average rate = - =-
t tfinal - tinitial
instantaneous rate = rate for specific instance in time 11
 For a graph of Concentration vs Time;
• The rate at any point can be measured by finding the
gradient.
• By finding tangents to the curve, the rates can be
determined for the specific time (instantaneous rate of
reaction).

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EXAMPLE 1
Consider the reversible gas-phase reaction between
ethylene and ozone at 303 K.
C2 H 4 ( g ) + O3 ( g ) ⎯⎯
→ C2 H 4O( g ) + O2 ( g )

Time (s) Concentration of Table shows the concentration

O3 (mol/L) of O3 at various times during
0.0 3.2x10-5 the first minute after introduce
10.0 2.42x10-5 C2H4 gas.
20.0 1.95x10-5
30.0 1.63x10-5

40.0 1.40x10-5
50.0 1.23x10-5

60.0 1.10x10-5
The concentration of O3 vs. time during its reaction with C2H4
The average rate over the first
60.0 s of the reaction.
[O3 ]
Rate = −
t
- (1.10x10 -5 - 3.2 10 -5 )M
Rate =
(60 - 0)s
Rate = 3.50 10 −7 Ms −1

Between the starting time 0.0s and

10.0 s, the average rate is;
[O3 ]
Rate = −
t
- (2.42 10-5 - 3.2 10-5 )M
Rate =
(10 - 0)s
Rate = 7.80 10 −7 Ms −1 14
 Between 50.0 s and 60.0s, the
average rate is rate;
[O3 ]
Rate = −
t
- (1.10 10-5 - 1.23 10-5 )M
Rate =
(60 - 50)s
Rate = 1.30 10 −7 Ms −1

Rate for first 10 sec Rate for last 10 sec

= 7.8 x 10-7 mol/L.S = 1.3 x 10-7 mol/L.S
 The earlier rate is six times as fast as the later rate.
 Thus, the rate decreases during the reaction.
 The rate of typical reaction is the fastest at the beginning because
reactants are at their highest concentration.
 Rate gradually decreases as reactants are being used up thus their 15
concentration decreases.
5.2 FACTORS AFFECTING RATE
OF REACTION
COLLISION THEORY

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 What is the Collision Theory ?
During a reaction, the particles of the reactants must
collide with each other, for bond breaking and then bond
formation to produce product.

Bond breaking : absorbs heat energy

Bond formation : releases heat energy

Those collisions which achieved a minimum activation

energy and with the correct orientation will result in a
reaction.
These collisions are called effective collisions.
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 EFFECTIVE COLLISION & ACTIVATION
ENERGY
If the particles collide with lower energy than activation energy
or at wrong orientation, it will not result in a reaction, is called
ineffective collisions.

Effective collisions?

✓ Those collisions which achieved a minimum activation energy

and with the correct orientation, will result in a reaction.

Activation energy?
✓ The activation energy, Ea is the minimum energy that the
reactant particles must have in order to react. 18
 COLLISION THEORY
1. The reactant molecules must collide with one another for a
reaction to occur.
2. NOT ALL collisions between reactant molecules will result in a
chemical reaction.
3. The reactant molecules must collide with sufficient energy and
the effective fraction of collision has energy greater than the Ea.
4. The molecules must collide in an orientation that can lead to
rearrangement of the atoms.

http://www.kscience.co.uk/animations/collision.htm

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 WHAT FACTORS AFFECT THE RATE OF
REACTION?
• Increased temperature
• Increase concentration of dissolved
reactants
• Increased pressure of gaseous reactants
• Increased surface area of solid reactants
• Use of a catalyst

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 EFFECT OF TEMPERATURE ON
RATE OF REACTION
Why does increased temperature increase the rate of reaction?

At a higher temperature, particles have more energy.

This means they move faster and are more likely to collide with
other particles.

When the particles collide, they do so with more energy, and so

the number of successful collisions increases.

The higher the temperature, the faster the reaction thus the
higher its rate of reaction. In many reactions, a rise in
temperature of 10°C causes the rate of reaction to
approximately double.

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 TEMPERATURE AND BATTERIES

• Why are batteries more likely to rundown

more quickly in cold weather?
• At low temperatures, the reaction that
generates the electric current proceeds
more slowly than at higher temperatures.
• This means batteries are less likely to
deliver enough current to meet demand.

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EFFECT OF CONCENTRATION ON RATE OF
REACTION
• Why does increased concentration increase the rate of reaction?
• At a higher concentration, there are more particles in the same
amount of space. This means that the particles are more likely to
collide and therefore more likely to react.
• The higher the concentration of a dissolved reactant, the faster
the rate of a reaction

lower concentration higher concentration

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 Effect of Concentration on the frequency of collisions

Therefore, increase the number of collisions and increase the

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reaction rate.
 SLOWER AND SLOWER!
• Reactions do not proceed at a steady rate. They start off at a certain
speed, then get slower and slower until they stop.
• As the reaction progresses, the concentration of reactants
decreases.
• This reduces the frequency of collisions between particles and so
the reaction slows down.

0% 25% 50% 75% 100%

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reactants
Percentage completion of reaction
product
 EFFECT OF PRESSURE ON RATE OF
REACTION
• Why does increasing the pressure of gaseous reactants increase
the rate of reaction?
• As the pressure increases, the space in which the gas particles
are moving becomes smaller.
• The gas particles become closer together, increasing the
frequency of collisions. This means that the particles are more
likely to react.

26
lower pressure higher pressure
 EFFECT OF SURFACE AREA ON RATE OF
REACTION
• Any reaction involving a solid can only take place on the surface
of the solid.
• If the solid is split into several pieces, the surface area increases.
What effect will this have on rate of reaction?
• This means that there is an increased area for the reactant
particles to collide with.
• The smaller the pieces, the larger the surface area thus more
collisions and a greater possibility of reaction.

low surface area high surface area 27

 USE OF CATALYST
• Catalysts are substances that speed up the rate of a reaction
without being used up in the reaction.
• Catalysts never produce more product – they just produce the
same amount more quickly.

Ea without Different catalysts work in

catalyst different ways, but mostly
they lower the reaction’s
energy (kJ)

activation energy (Ea).

Ea with
catalyst
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reaction (time)
5.3 RATE LAW AND ORDER OF
REACTION

RATE LAW FOR ZERO, FIRST AND SECOND ORDER OF

REACTIONS

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 DIFFERENTIAL RATE EQUATION

Consider the following general equation:

aA + bB cC

Differential rate equation should be expressed as :

1  d[A]  1  d[B]  1 d[C]

Rate =  −  = − =
a  dt  b  dt  c dt

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EXAMPLE 2

2N2O5(g) → 4NO2(g)+ O2(g)

Write the differential rate equation for the above equation.
Solution:

1  d[N2O5 ]  1  d[NO2 ]   d[O2 ] 

Rate =  − =  = 
2 dt  4  dt   dt 

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EXAMPLE 3

2O3 ( g ) → 3O2 ( g )
Write the differential rate equation for the above equation.
Solution:
1 d [O3 ] 1 d [O2 ]
rate = − =
2 dt 3 dt
OR

d [O3 ] 2 d [O2 ]
rate = − =
dt 3 dt
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 THE RATE LAW
The rate law expresses the relationship of the rate of a reaction to
the rate constant and the concentrations of the reactants raised to
some powers.
Consider the following general equation:

aA + bB cC + dD

Rate = k [A]x[B]y

reaction is xth order in A

reaction is yth order in B

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EXAMPLE 4

rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1

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 F2 (g) + 2ClO2 (g) → 2FClO2 (g)

rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] constant →Rate doubles → x = 1

Quadruple [ClO2] with [F2] constant → Rate quadruples → y=1

rate = k [F2][ClO2]
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• Rate laws are always determined experimentally unless you have
been told a rate-limiting or slow step.

• Reaction order is always defined in terms of reactant (not product)

concentrations.

• The order of a reactant is not related to the stoichiometric

coefficient of the reactant in the balanced chemical equation.

1 F2 (g) + 2ClO2 (g) → 2FClO2 (g)

rate = k [F2][ClO2]

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 EXAMPLE 5
Determine the rate law and calculate the rate constant for the following
reaction from the following data:
S2O82- (aq) + 3I- (aq) → 2SO42- (aq) + I3- (aq)

Initial
Experiment [S2O82-] [I-]
Rate (M/s) rate = k [S2O82-]x[I-]y
1 0.08 0.034 2.2 x 10-4 y=1

2 0.08 0.017 1.1 x 10-4 x=1

rate = k [S2O82-][I-]
3 0.16 0.017 2.2 x 10-4

Double [I-], rate doubles (experiment 1 & 2)

Double [S2O82-], rate doubles (experiment 2 & 3)

rate 2.2 x 10-4 M/s

k= = = 0.08/M•s 37

[S2O8 ][I ]
2- -
(0.08 M)(0.034 M)
 THE ORDER OF REACTION

• Indicate the number of concentration factors

in the rate equation.
• Can only be determined experimentally.
• It shows the exact dependence of rate on
concentration.
• NOT from the number of moles as written in
the stoichiometric equation.

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For a reaction with a single reactant A
First order reaction:
- Rate is directly proportional to [A]
rate = k[A]

Second order reaction:

- Rate is directly proportional to the
square of [A]
rate = k[A]2

Zero order reaction:

- the rate is not dependent on [A]

rate = k[A]0 = k (1) = k

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 THE OVERALL REACTION ORDER

Rate = k [ A ]x [B ]y

The overall order of reaction = sum of the individual orders with

respect to each reactant in the rate law = x + y

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