CHM 271

CHAPTER 5
CHEMICAL KINETICS
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 CHAPTER 5 : CHEMICAL KINETICS
5.1 Rates of reaction
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
 CHAPTER 5 : CHEMICAL KINETICS
5.5 Relationship between rate and temperature
5.5.1 Arrhenius equation
5.5.2 Determination of activation energy using Arrhenius equation (graphical method & 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
5.7.1 Homogeneous and heterogeneous catalysis
5.7.2 Enzyme catalysis
 INTRODUCTION

Chemical Kinetics or Reaction Kinetics

The study of the rate of chemical reactions

Basically….
How fast does achemical
reaction occur?
 RATE OF REACTION
DEFINITION A measure of the change in the concentration of a
reactant or product in a given time.

∆
rate 
∆𝑡

Unit 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
=
𝑡𝑖𝑚𝑒

𝑚𝑜𝑙ൗ 𝑚𝑜𝑙 𝑑𝑚∗3

= 𝐿
@
𝑠𝑒𝑐𝑜𝑛𝑑 𝑠𝑒𝑐𝑜𝑛𝑑

= mol L-1 s-1 @ Ms-1

 RATE OF REACTION
 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 ∝
time
 RATE OF REACTION

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

 A B

time

[A]
rate = -
t

[B]
rate =
t
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  
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 =

 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
 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).
EXAMPLE 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 of O3

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

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

 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 last 10 sec

Rate for first 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
concentration decreases.
 DIFFERENTIAL RATE EQUATION

Consider the following general equation:

aA + bB cC
Differential rate equation should be expressed as :
1 ∆𝐴 1 ∆𝐵 1∆𝐶 1 ∆𝐷
𝑟𝑎𝑡𝑒 = − =− = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡
EXAMPLE

2N2O5(g) 4NO2(g) O2(g)

Write the differential rate equation for the above equation.

SOLUTION
1 ∆ N2O5 1 ∆ NO2 1 ∆ O2
𝑟𝑎𝑡𝑒 = − = =
2 ∆𝑡 4 ∆𝑡 1 ∆𝑡
EXAMPLE

2O 3 ( g )  3O 2 ( g )
Write the differential rate equation for the above equation.

SOLUTION
1 ∆ 𝑂3 1 ∆ 𝑂2
𝑟𝑎𝑡𝑒 = − =
2 ∆𝑡 3 ∆𝑡
FACTORS AFFECTING RATE OF REACTION

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.
EFFECTIVE COLLISION & ACTIVATION ENERGY
INEFFECTIVE COLLISIONS
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.
 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
FACTORS AFFECTING 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
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.
 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.
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

 Effect of Concentration on the frequency of collisions

Therefore, increase the number of collisions and increase

the 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%

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.

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

 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
activation energy (Ea).
energy (kJ)

Ea with
catalyst

reaction (time)
 RATE LAW AND ORDER OF REACTION

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
x & y is integers = 0, 1 , 2 ….
 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
 THE OVERALL REACTION ORDER

EXAMPLE
2NO + 2H2 → N2 + 2H2O
The rate equation is:

Rate = k[NO]2[H2]

 The reaction is second order with respect to NO,

 The reaction is first order with respect to H2
 Overall order of reaction is the third order.
 UNIT FOR RATE CONSTANT, k

 Unit of k is obtained as follows;

 m & n is the order of reaction for A & B respectively.

 UNIT FOR RATE CONSTANT, k

EXAMPLE
Predict the unit of rate constant (k) in the following rate law
a) Rate = k[A]
b) Rate = k[A][B]
c) Rate = k[A][B]2

SOLUTION
a) S-1
b) M-1S-1
c) M-2S-1
EXAMPLE

rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
 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]
 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]
EXAMPLE
Determine the rate law and the rate constant for the following
reaction from given data:
S2O82- (aq) + 3I- (aq) → 2SO42- (aq) + I3- (aq)
[S2O 2-] Initial
Experiment [I-]
8 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
3 0.16 0.017 2.2 x 10-4 rate = k [S2O82-][I-]
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
[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.
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

METHODS TO DETERMINE ORDER OF REACTION

1. Initial Rate
2. Integrated Rate Law
3. Half- Life
 INITIAL RATE METHOD

To find the reaction orders by initial rate method,

 Run a series of experiments

 Each of the experiments have a different set of reactant
concentration
 From each experiments, obtain an initial rate.
 EXAMPLE
The results shown below are obtained for the reaction between
A and B. Determine the rate equation for the reaction between
A and B.

Experiment Concentration Initial rate

(mol L-1) (mol L-1 s-1)
[A] [B]
1 0.0575 0.0216 8.21x10-3
2 0.0713 0.0216 1.26x10-2
3 0.0575 0.0333 1.26x10-2
SOLUTION
Calculating x in [A]x; we take the ratio of the rate laws for two
experiment 1 and 2, in which [A] varies but [B] is constant:

That is, 0.652 = 0.806x

Log 0.652 = x * log 0.806 x = 1.99  2
Thus, the reaction is Second order with respect to A
 SOLUTION
Calculating y in [B] ; we take the ratio of the
y

rate laws for two experiment 1 and 3, in which [B] varies

but [A] is constant

That is, 0.652 = 0.649y

Log 0.652 = y x log 0.649
y ≈ 1
• Hence, the reaction is first order with respect to B.
• The rate equation is ra te  k [A]2 [B ]
 PRACTICE

The reaction between C and D is represented as follows :

C+D→ E
The experiment results are shown in the table below.
Determine the rate equation for the reaction between C and
D.
Initial concentration (M) Time The change in
Experiment interval concentration of
[C] [D] (minutes) C (M)

1 0.05 1.0 30 2.5 x 10-3

2 0.05 2.0 30 1.0 x 10-2

3 0.1 1.0 120 5.0 x 10-3

46
 INTEGRATED RATE LAW METHOD
0th ORDER Equating the rate law with differential rate
A ⟶ products equation give :
∆ A
rate = k[A]0 - = k[A]0 = k
∆𝑡
∆ A [A]t − [A]0= - k𝑡
Rate = -
∆𝑡
[A]t= - k𝒕 + [A]0
[A]t = [A] at time t
[A]o = initial concentration
∆𝑡 = 𝑡 – 𝑡0 = t ; 𝑡0 = 0

[A]t = - k t + [A]o

y mx + c
 INTEGRATED RATE LAW METHOD
1st ORDER 1. equating the rate law with differential
A ⟶ products rate equation will give

rate = k[A] ∆ A
- = k[A]
∆𝑡
∆ A
Rate = - 1
∆ A = - k ∆𝑡
∆𝑡
A

2. Let [A]t = [A] at time t & [A]o = initial concentration,

integrating within the limit:
[𝑨]𝒕 𝟏 𝑡
‫∆ ]𝑨[ ]𝑨[׬‬ A = - k ‫׬‬0 ∆𝑡
𝟎

ln [A]t - ln[A]0 = - kt
ln [A]t = - kt + ln[A]0
 When ln [A]t is plotted against t, a sloping straight line is
obtained.

ln [A]t = - k t + ln [A]o

y m x + c

[A]0
 The graph of ln against t yields a sloping straight lines
[A]t
that passes through the origin point. [A]
ln [A]0
ln[ A]t  ln[ A]o  kt t

ln[ A]0  ln[ A]t  kt

gradient= k
[A]0
ln = kt
[A]t
t
y m x;c=0
 INTEGRATED RATE LAW METHOD
2nd ORDER Equating the rate law with differential rate
A ⟶ products equation will give
∆ A
rate = k[A]2 - = k[A]2
∆𝑡
∆ A 1
∆ A =-k
Rate = -
∆𝑡 [A]2
[A]t = [A] at time t ∆𝑡
[A]o = initial concentration [A]t − [A]0
=-k𝑡
∆𝑡 = 𝑡 – 𝑡0 = t ; 𝑡0 = 0 [A] 2

1 1
− =-k𝑡
[A]0 [A]t
𝟏 𝟏
= k𝒕+
[A]t [A]0
y = mx + c
 HALF-LIFE METHOD
Half-life, t½,
is the time required for the concentration of a reactant to decrease
to half of its initial concentration.

t½ = t when

[A]t = [A]0/2
 HALF-LIFE METHOD
t = t½ when [A]t = [A]0/2
0th ORDER 1st ORDER 2nd ORDER
[A]t= - k𝑡 + [A]0 ln [A]t = - kt + ln[A]0
1
= k𝑡 +
1
[A]t [A]0
[A]0 [A]0
= - k𝑡½ + ln = - k𝑡½ + 1 1
2 2 = k𝑡½ +
[A]0 ln[A]0 [A]0ൗ [A]0
2

[A]0 [A]0 2 1
𝒕½ = k𝑡½ = ln k𝑡½ = -
𝟐𝒌 [A]0ൗ [A]0 [A]0
2
1
k𝑡½ = ln 2 k𝑡½ =
[A]0
ln 2
𝒕½ = 𝒕½ =
𝟏
𝒌 k[A]0
 DETERMINING ORDER OF REACTIONS
Half Life (Graphically)

log t½

Slope = 1(Zero order)

Slope = 0 (First order)

Slope = -1 (Second order)

log [reactant]o
 Summary of the Kinetics

Order of Half life, Unit of k

Rate Law Integrated Rate Law
Reaction t1/2

[A]0 Ms-1
Zeroth Rate = k [A]t = [A]0 - kt
2𝑘
ln 2 s-1
First Rate = k[A] ln [A]t = ln[A]0 - kt 𝑘
Second Rate = k[A]2 1 1
= kt + 1
M-1s-1
[A]t [A]0 k[A]0
Rate = k[A][B]
 EXERCISE
1. The conversion of cyclopropane to propene in the gas phase is a first
order reaction with a rate constant of 6.7 x 10-4 s-1 at 500°C.
a) If the initial concentration of cyclopropane is 0.25M,what is the
concentration after 8.8 minutes? 0.18M

b) How long in minutes will it take for the concentration of 13 min

cyclopropane to decrease from 0.25M to 0.15M?

2. The rate for decomposition of SO2 is 2.4 x 10-4 MS-1 when the
concentration of SO2 is 1.0 x 10-3 M. if the reaction is first order, 0.24 s-1 ;
calculate the rate constant and half life for thereaction. 2.89 s

3. The decomposition of NOCl is second order with the rate constant

0.05M-1S-1. Determine the half life for NOCl if its initial concentration
is 0.4M. 50s

4. If k is 4.0 x 10-6 M-1S-1 and the initial concentration of HI is 2.0 x 10-2 M,

determine the half life of thereaction
1.25 x 107 s
RELATION BETWEEN RATE AND TEMPERATURE
A+B AB+ C+D
Exothermic Reaction Endothermic Reaction

The activation ener gy (E a ) is the minimum amount of

energy required to initiate a chemical reaction.
 How Temperature and Catalysts Affect Reaction Rates

Consider Arrhenius’ Equation

Temperature
k= A e -Ea/RT

Frequency Activation Gas constant

energy 8.314 J/mol • K
of collisions
The larger the temperature, the smaller the negative term.
The smaller negative term, the larger the value once you have
applied ex.
Therefore, INCREASING TEMPERATURE will INCREASE THE
REACTION RATE.
 Determining the Activation Energy
GRAPHICALLY

 take natural log of both sides of the Arrhenius equation:

ln k

ln A
Slope = -Ea/R

y = m x + c

1/T

When k is determined experimentally at several temperatures,

Ea can be calculated from the slope of a plot of ln k vs. 1/T.
 Determining the Activation Energy
CALCULATION

If we have two different k values at different temperatures,

you can combine the two reactions to give:

60
 EXERCISE
1. For the reaction HI + CH3 → CH4 + I, the rate constant is
1.7 x 10-5 dm3 mol-1 s-1 at 430 K and 9.6 x 10-5 dm3 mol-1 s-1 at 450 K. Determine
the activation energy for thereaction.
139.25 kJ/mol

2. For a reaction, the frequency factor is 8.3 x 108 M-1S-1 and Ea is 28.9 kJ/mol. If
the reaction is a second order, what is the rate constant for the reaction at 30
°C?
8.65 x 103 M-1S-1

3. Given rate law, Rate = k[CO][NO2]. If the frequency factor for the reaction at
25°C is 5.0 x 108 M-1S-1 and the Ea is 116 kJ/mol, what is the rate constant at
25°C and at 100°C?
2.32 x 10-12 M-1S-1, 2.84 x 10-8 M-1S-1
 REACTION MECHANISM
 The overall progress of a chemical reaction can be represented
at the molecular level by a series of simple elementa r y
steps or elem entar y reactions.

 The rate law for an elementary step is written directly from

that step
2NO (g) + O2 (g) 2NO2 (g)

N2O2 is detected during the

reaction!
Elementary step: NO + NO N2O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2 62
 REACTION MECHANISM
REACTION MECHANISM
the sequence of elementary steps that leads to product formation
 Tell what happens on the molecular level, and in what order
 Tell us which steps in a reaction are fast and slow.

ELEMENTARY STEPS
Series of simple reaction that represent the progress of the overall
reaction at the molecular level which makes it clear exactly how the
various bonds are broken and made.

RATE DETERMINING STEP

The steps which is slower than all others (slowest step)
 The overall rate of a reaction is controlled by the rate of the
slowest step.
 REACTION MECHANISM
MOLECULARITY
Number of molecules reacting in one elementary steps
 Unimolecular→ one reacting molecule
 Bimolecular → two molecules involves
 Termolecular → three molecules involves
 REACTION MECHANISM
INTERMEDIATES
Species that appear in a reaction mechanism but not in the overall
balanced equation.
 An intermediate is always formed in an early elementary step
and consumed in a later elementary step.

EXAMPLE

CATALYST
Species that appear in the elementary steps but not in the
overall equations.
 Species that is present at the start of the reaction and at
its completion.
Determining the rate law Slow → Fast Step

Step 1: NO2 + NO2 NO + NO3 (slow)

Step 2: NO3 + CO NO2 + CO2 (fast)

Overall: NO2 + CO NO + CO2

Intermediate = NO3

Rate = k[NO2]2

As CO is not involved in the slow, rate-determining step, it

does not appear in the rate law.
 Fast Reversible→ Slow Step

k f [NO][Br2 ]  k r [NOBr2 ]
fast
kf
[NOBr2 ]  [NO][Br2 ]
kr

slow  k1[NOBr2 ][NO]

k1k f
substitute fast in slow
 [NO][Br2 ][NO]
kr
 k[NO] 2 [Br ]
2
 EXERCISE
2 NO2 (g) + CO(g) → NO (g) + CO2 (g)
The reaction between NO2 (g) and CO(g) is represented
above. The elementary steps of a proposed reaction
mechanism are represented below.

Step 1: 2 NO2 (g) → NO(g) + NO3 (g) (slow)

Step 2: NO3 (g) + CO(g) → NO2 (g) + CO2 (g) (fast)

Predict the rate law for the reaction mechanism above.

 EXERCISE
2 NO(g) + O2 (g) → 2 NO2 (g)
Consider the following mechanism for the reaction represented
above.

Step 1. 2NO ⇄ N2O2 (fast, reversible)

Step 2. N2O2 + O2 → 2 NO2 (slow)

Predict the rate law for the reaction mechanism above.

 CATALYTIC KINETICS
A catalyst is a substance that increases the rate of a
chemical reaction by lowering the activation energy.
k = A • exp( -Ea/RT )
uncatalyzed catalyzed

Ea k

rate > rate

catalyzed uncatalyzed
Ea‘< Ea
Effect of a Catalyst in a Reaction
 Properties of Catalyst

 Provide an alternative reaction pathway by lowering the

activation energy for both the forward and reverse
reactions
 Chemically unchanged at the end of reaction
 Catalyst which decrease the reaction rate
– negative catalyst (inhibitor)
 May react to form an intermediate with the reactant but
it is regenerated in a subsequent step, so it is not
consumed in the reaction
 Has an optimum temperature
 Only a small amount of catalyst is required
 Types of Catalyst

HOMOGENEOUS
Catalyst which present in the same phase as the reacting substances

HETEROGENEOUS
Catalyst which present in the different phase as the reacting
substances
 CATALYSIS
DEFINITION
a process in which the rate and/or the outcome of the reaction is
influenced by the presence of a substance (the catalyst)

HOMOGENEOUS
the reactants and the catalysts are dispersed in a single phase,
usually liquid.
 Acid catalysis
 Base catalysis

HETEROGENEOUS
The reactants and the catalysts are in different phases.
 Haber synthesis of ammonia
 Ostwald process in the production of nitric acid
 Catalytic converters 74
 HABER PROCESS

Fe/Al2O3/K2O
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst
 OSTWALD PROCESS
Pt catalyst
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
2NO (g) + O2 (g) 2NO2 (g)
2NO2 (g) + H2O (l) HNO2 (aq) + HNO3 (aq)

Hot Pt wire
over NH3 solution

Pt-Rh catalysts used

in Ostwald process
 CATALYTIC CONVERTERS

catalytic
CO + Unburned Hydrocarbons + O 2 converter
CO2 + H2O

catalytic
2NO + 2NO 2 converter 2N2 + 3O2
 ENZYME CATALYSIS
 Enzymes are biological catalyst.
 Highly specific.
 Acts only on certain molecules called substrate
(reactants).
 Typically a large protein molecule that contain one or
more active sites.

 The substrate fits into the

active site of the enzyme
much like a key fits into a
lock.
 Enzyme molecule has a fair
amount of structural
flexibility & can modify its
shape to accommodate
more than one type of 78
 “Knowledge is
power,
community is
strength & attitude
is everything”

“Knowledge Shared
= Knowledge 2 ”
79