CHAPTER 1:

REACTION KINETICS

1
 CHAPTER 1:
REACTION KINETICS
1.1 Reaction Rate
1.2 Collision Theory
1.3 Factors Affecting
Reaction Rate
2
1.1 REACTION RATE

3
 LEARNING OUTCOME
SK025 1.1 (a)

 Define reaction rate

 Reaction Rate
 Definition: Changes in concentrations of reactants (or
products) as a function of time
 Consider a reaction :
A  B
When reaction occur, the concentration of A is decreased
while the concentration of B increased with time.
 As reaction proceed:
[ REACTANT ]  and [ PRODUCT ] 
 LEARNING OUTCOME
SK025 1.1 (b)

 Write differential rate equation

 Differential Rate Equation
 Shows the relationship between the rate of disappearance of
reactants and formation of products.

aA+bB cC+dD

 Negative sign indicates [A] and [B] decreases with time.

 Positive sign indicates [C] and [D] increases with time.
 KEEP IN MIND
2A B

   

 Two moles of A disappear for each mole of B that

formed
 Unit of Reaction Rate
aA+bB cC+dD
 

 Unit : mol L–1s–1 or mol dm−3 s−1 or Ms–1

 Unit of time : s (seconds), min, hr, day, year
 Example : mol dm–3 min–1
 1

Write the differential rate equation for the

following reaction.

(a) CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g)

(b) N2 (g) + 3H2 (g)  2NH3 (g)
 1
(a) CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g)

(b) N2 (g) + 3H2 (g)  2NH3 (g)

 
 LEARNING OUTCOME
SK025 1.1 (c)

 Determine reaction rate based on

differential rate equation.
 2 2
Dinitrogen pentoxide gas decomposes to nitrogen
dioxide gas and oxygen gas according to the following
balance equation below.
2N2O5 (g)  4NO2 (g) + O2 (g)
(a) Write the differential rate equation for the
dissociation of N2O5 gas.
(b) If the rate of disappearance of N2O5 gas is
1.0 x 102 Ms-1, what is the rate of formation of NO2
gas under the same conditions of temperature and
 2

2N2O5 (g)  4NO2 (g) + O2 (g)

 
(a)
 

= 2 x 1.0 x 102 Ms–1

= 2.0 x 102 Ms–1
 LEARNING OUTCOME
SK025 1.1 (d)

 Define:
i. rate law
ii. order of reaction
iii. half-life, t1/2

Remarks:
Rate law is also known as rate equation.
 Rate Law / Rate Equation
 An equation that relates the rate of a reaction to the rate constant and
the concentrations of the reactants raised to some powers
Example: aA + bB  cC + dD
Rate = k [A]m [B]n
Where :
[A]= concentration of A [B]= concentration of B
k = rate constant
m = order of reactions with respect to A
n = order of reaction with respect to B
m + n = overall order of reaction
 Order of Reaction
aA+bB cC+dD
Rate = k [A]x [B]y
 Exponent of x (0, 1, 2,3, ½, ¾ and etc ) and
y (0, 1, 2, 3, ½, ¾ and etc)
 Define how the rate affected by reactant
concentration

 The reaction orders cannot be predicted from the

stoichiometry of the balanced equation; it must be
determined experimentally.
 KEEP IN MIND
 Order of a reactant is not related to stoichiometric coefficient
of
reactant in the balanced chemical equation.
EXAMPLE:
F2 (g) + 2ClO2 (g) 2FClO2 (g)
rate = k [F2][ClO2]1
 Can only be determined experimentally
 May be integral (i.e., 1, 2, 3,…), zero, fractional, decimal or /and
negative
 3 3
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)
Rate = k[NO]2[H2]

The reaction is:

 Second order with respect to NO
 First order with respect to H2
 Overall reaction = third order reaction
 1
For each of the following reactions, determine the reaction order
with respect to each reactant and the overall order from the given
rate law:

(a) 2NO (g) + O2 (g)  2NO2 (g)

Rate = k [NO]2[O2]

(b) CH3CHO (g)  CH4 (g) + CO (g)

3/2
Rate = k [CH3CHO]

(c) H2O2 (aq) + 3I– (aq) + H+ (aq)  I3– (aq) + 2H2O (l)
Rate = k [H2O2][I–] ANSWER:
a) second order in NO, first order in O2, third order overall b) 3/2 order in CH3CHO, 3/2 order overall
c) first order in H O , first order in I-, zero order in H+, second order overall
 Rate Constnt (k)
aA + bB cC + dD
Rate = k [A]x [B]y

 Proportionality constant for a given reaction and

temperature
 Does not change as reaction proceeds
 You can always determine
the unit of k mathematically

4
What is the unit of k for a third order reaction?
 

 
 2
A  products
Without consulting textbooks, give the units of
the rate constants for reactions with the
following orders: (Time: in s)
(a) First order
(b) Second order
(c) Third order
(d) 5/2 order
ANSWER:
a) k = s-1 b) k = M-1 s-1 c) k = M-2 s-1 d) k = M-3/2 s-1
Overall Reaction Order From The
Unit of k
Rate = k [A]x
Overall Units of k
Reaction Order (t in seconds)

0 Mol L–1s–1 or M s–1

1 s–1
2 L mol–1s–1 or M–1s–1
 Half – life ()
 Time required for the concentration of a reactant to
decrease
to half of its initial concentration
   
 for Zero Order Reaction

 t½ directly proportional to the initial

concentration of the reactant
 6 5
A  products
Determine the half-life of substance A if the rate
constant is 0.00624 M s-1 and its original concentration
is 1.2 M .
 5
The reaction is zero order reaction

[A]o
t½ =
2k
1.2 M
t½ = 2(0.00624 M s-1)

t½ = 96.15 s
 for First Order Reaction

 t½ is independent of the initial concentration

of the reactant.
 6
What is the half–life (in min) of N2O5 if it
decomposes with a rate constant of
5.7 x 10–4 s–1?
 6
The unit of k = s–1  First order reaction
ln2
t½ =
k
0.693
=
5.7 x 10–4 s–1
= 1216 s

= 20.27 min
for Second Order Reaction

 t½ inversely proportional to the

initial
concentration of the reactant.
 LEARNING OUTCOME
SK025 1.1 (e)

 Write rate law with respect to the

order of reaction.
Rate Law for Zero Order Reaction
If the reaction is; A  Products
Rate = k [A]o
Rate = k
 Zero order in A
 Zero order overall
 Quite common in metal–catalyzed and
biochemical processes
 Rate is not dependent on the concentration
of the reactant
Rate Law for Zero Order Reaction
 If [A] is DOUBLE  rate is NOT AFFECTED
[ A ] = [ 2A ]
Rate = k [2A]0
Rate = k

36
Rate Law for First Order Reaction
If the reaction is; A  Products
Rate = k [A]
 First order in A
 First order overall
 Example: Radioactive reaction (uranium,
plutonium etc)
 Rate is dependent on the concentration of the reactant.
Doubling [A], the rate will increase by a factor of 2/
increase 2-fold / double.
Rate Law for First Order Reaction
 If [A] is DOUBLE  rate is DOUBLE
[ A ] = [ 2A ]
Rate = k [2A]
Rate = 2k [A]
Rate Law for Second Order Reaction
If the reaction is; A  Products
Rate = k [A]2
 Second order in A
 Second order overall
 Rate is dependent on the concentration of the reactant.
Doubling [A], the rate will increase by a
factor of 4 / 4-fold
Rate Law for Second Order Reaction
 If [A] is DOUBLE  rate is QUADRUPLES
[ A ] = [ 2A ]
Rate = k [2A]2
Rate = 4k [A]2

40
 LEARNING OUTCOME
SK025 1.1 (f)

 Write the integrated rate equation for zero,

first and second order reactions.

SK025 1.1 (h)

 Perform calculation using integrated rate equations.

 Integrated Rate Law
 The relationship between the
concentration of the reactants and
time.
 May be used to determine the rate
constant and half-life.
Integrated Rate Law : Zero Order
Reaction
If the reaction is; A  Products
[A]o – [A]t = kt
OR
[A]t = [A]o – kt
Where:
[A]o = Initial concentration
[A]t = Concentration at particular time
t = Time of reaction
k = Rate constant
 7
A  products
A reaction starts with an initial
concentration of reactant of 1.00 M and
has a rate constant of 1.65 x 10-5 M s-1. What
is the concentration of the reactant after
100 minute ?
 7
The reaction is zero order reaction; [A]t– [A]o = – kt
t = 100 minute = 6000 s

[A]t = – k t + [A]o
[A]t = –(1.65 x 10-5 M s-1)(6000 s) + 1.00 M
[A]t = 0.901 M
 Integrated Rate Law : First Order
Reaction
If the reaction is; A  Products
 

=
Where:
[A]o = Initial concentration
[A]t = Concentration at particular time
t = Time of reaction
k = Rate constant
 8
N2O5 decomposes into N2O4 and O2.
2N2O5 (g)  2N2O4 (g) + O2 (g)
At 45 oC, k = 6.22 x 10–4 s–1.
If the initial concentration of N2O5 in a carbon
tetrachloride solution at 45oC is 0.500 M, what
will the concentration be after exactly one hour?
 8
2N2O5 (g)  2N2O4 (g) + O2 (g)
[N2O5]o
The reaction is first–order overall; ln = kt
[N2O5]t

k = 6.22 x 10–4 s–1

t = 1 hr x 3600 s/hr = 3600 s
[N2O5]o = 0.500 M
[N2O5]t = ?
 8
[N2O5]o
ln =kt
[N2O5]t
0.500
ln = 6.22 x 10–4 s–1 x 3600 s
[N2O5]t
0.500
= 9.3858
[N2O5]t
[N2O5]t = 0.0533 M
Integrated Rate Law : Second Order Reaction

If the reaction is; A  Products

 

Where:
[A]o = Initial concentration
[A]t = Concentration at particular time
t = Time of reaction
k = Rate constant
 9
Iodine atoms combine to form molecular iodine
in the gas phase
I (g) + I (g)  I2 (g)
The rate constant of the reaction is
7.0 x 109 M-1s-1 at 23oC.
If the initial concentration of I was 0.086 M,
calculate the concentration after 2.0 min.
 9
I (g) + I (g)  I2 (g)
1 1
The reaction is second–order overall; = + kt
[I]t [I]o
k = 7.0 x 109 M–1s–1
t = 2.0 min x 60 s/min = 120 s
[I]o = 0.086 M
[I]t = ?
 9
1 1
= +kt
[I]t [I]o
1 1 + (7.0 x 10 9
M s ) x 120s
–1 –1
= 0.086 M
[I]t
= 8.4 x 1011 M–1
[I]t = 1.190 x 10–12 M
 3
The reaction 2A B is first order in A
with a rate constant of 2.8 x 10–2 s–1 at 80oC.
How long will it take for A to decrease from
0.88 M to 0.14 M ?
 3
2A  B  first order reaction
[A]o = 0.88 M [A]o
ln = kt
[A]t = 0.14 M [A]t
k = 2.8 x 10–2 s-1
0.88 M
[A]o ln
ln 0.14 M
[A]t t =
t = 2.8 x 10–2 s-1
k
= 66 s
 LEARNING OUTCOME
SK025 1.1 (g)

 Determine the order of reaction involving

single reactant using
 Initial rate method
 Half-life based on graph of concentration
against time
 Linear graph method based on the
integrated rate equation and rate law
METHODS TO DETERMINE ORDER OF REACTION :

• INITIAL RATE METHOD

1

• HALF-LIFE GRAPH METHOD

2

• LINEAR GRAPH METHOD

3
 1. Initial Rate Method
1. Use concentration measurement
to find initial rate

2. Use initial rates from several

experiments to find reaction orders

3. Use these values to calculate

rate constant
 10
Determine the rate law and calculate the rate
constant for the following reaction from the
following data:
F2 (g) + 2ClO2 (g) 2FClO2 (g)

Experiment [F2] [ClO2] Initial Rate

(M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3
 10
Experiment [F2] [ClO2] Initial Rate
(M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3

Rate = k [F2]x [ClO2]y

 Find order in F2 with [ClO2] constant:
Rate 3 k[F2]x[ClO2]y 2.4 x 10-3 k[0.2]x[0.01]y
=
Rate 1 = k[F2]x[ClO2]y 1.2 x 10 -3
k[0.1]x[0.01]y
2.4 x 10-3 (0.2)x
= x =1
1.2 x 10-3 (0.1)x
 first order in F2
(2.0)1 = (2.0)x
 10
Experiment [F2] [ClO2] Initial Rate
(M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3

Rate = k[F2]x[ClO2]y
 Find order in ClO2 with [F2] constant:
Rate 2 k[F2]x[ClO2]y 4.8 x 10-3 k[0.1]x[0.04]y
= =
Rate 1 k[F2] [ClO2]
x y 1.2 x 10 k[0.1]x[0.01]y
-3

4.8 x 10-3 (0.04)y y =1

1.2 x 10-3 = (0.01)y
 first order in ClO2
(4.0)1 = (4.0)y
 10
Rate = k [F2]x [ClO2]y
x = 1, y = 1 rate = k [F2][ClO2]

 Use any experiment data (example Exp. 1) to find k

1.2 x 10-3 M s–1 = k (0.1 M)(0.01 M)

k = 1.2 M–1s–1
 4
Consider the reaction between nitrogen dioxide, NO2
and carbon monoxide, CO :
NO2 (g) + CO (g) → NO (g) + CO2 (g)
The initial rate of the reaction is measured at several
different concentrations of the reactants with the
following results :
Experiment [ NO2 ] / M [ CO ] / M Initial rate (Ms-1)

1 0.10 0.10 0.0021

2 0.20 0.10 0.0082
3 0.20 0.20 0.0083
4 0.40 0.10 0.033
From the data, determine the rate law and rate constant
for the reaction. 63
 4
Rate = k[NO2]x [CO]y
 Find order in F2 with [ClO2] constant:
Rate 2 k [NO2]x [CO]y 0.0082 k [0.20]x [0.10]y
= =
Rate 1 k[NO2]x [CO]y 0.0021 k [0.10]x [0.10]y
0.0082 (0.20)x
0.0021 = (0.10)x
3.9 = (2.0)x
x =2
 Second order in NO2
 4
 Find order in NO2 with [CO] constant:
Rate 3 k [NO2]x [CO]y 0.0083 k[0.20]x[0.20]y
= =
Rate 2 k [NO2] [CO]
x y 0.0082 k[0.20] x
[0.10] y

0.0083 = (0.20)y
0.0082 (0.10)y
1.01 = (2.0)y
y = 0.01
y = 0
 Zero order in CO
 4
Rate = k [NO2]x [CO]y

x = 2, y = 0 Rate = k [NO2]2

 Use any experiment data (example Exp. 1) to find k

0.0021 M s–1 = k (0.10 M)2

k = 0.21 M –1s –1
2. Half-life Graph Method
The reaction order also can be
determined by using the half-life equation
!
How ?

By plotting graph concentration against time !

 look for the relationship between 1st half-life
with 2nd half-life

Why ?

Let’ discuss !
 11
From the following data determine the order
of the reaction, half-life and the rate constant.
TIME (min) [ C2H5I ] (M)
0 1.00
25 0.78
50 0.61
75 0.47
100 0.37
150 0.22
200 0.14
250 0.08
 11
 Plot a graph [ C2H5I ] vs time
 Determine the 1st half-life and 2nd half-life
from the graph
 Determine the order of the reaction
 Determine the rate constant, k
 1.00

0.90
Graph [ C2H5I ] against Time
0.80
1st t1/2 = 70
0.70 2nd t1/2 = 70 min
0.60
1nd t1/2 = 2nd t1/2
 1st order reaction
[C2H5], M

0.50

0.40

0.30

0.20

0.10

0.00
0 25 50 75 100 125 150 175 200 225 250

Time, (min)
70 140
1st t1/2 2nd t1/2
 11
1st half-life = 2nd half-life,
t½ (II) = t½ (I)
 First order reaction
Half-life = 70 minute (from the graph)

t½ = ln2
k
ln2 0.693
k = = = 9.9 x 10-3 min-1
t½ 70 min
3. Linear Graph Method
The reaction order also can be
determined by using the integrated
rate law or rate law!

How ?
By plotting the graph !
 look for the linear graph

Which graph ?
Which one ???

I don’t know. Just

try-and-error!
How ?
By plotting the graph !
 look for the linear graph
Concentration-Time
Equation (Integrated
Order Rate Law Rate Law)

0 rate = k [A] = [A]o – kt

[A]o
1 rate = k [A] ln = kt
[A]
1 1
2 rate = k [A]2 = + kt
[A] [A]o
   
Plot ln[reactant] vs. time:
 Linear graph obtained
 First order reaction

Plot 1/[reactant] vs. time:

 Linear graph obtained
 Second order reaction

Plot [reactant] vs. time:

 Linear graph obtained
 Zero order reaction
 12
Ethyl iodide (C2H5I) decomposes at a certain
temperature in the gas phase as follows:
C2H5I (g)  C2H4 (g) + HI (g)
From the following data determine the order
of the reaction and the rate constant.
TIME (min) [ C2H5I ] (M)
0 0.36
15 0.30
30 0.25
48 0.19
75 0.13
 12
TIME (min) [ C2H5I ] (M) ln[C2H5I] 1/[C2H5I]

0 0.36 – 1.02 2.78

15 0.30 – 1.20 3.33

30 0.25 – 1.39 4.00

48 0.19 – 1.66 5.26

75 0.13 – 2.04 7.69

 12
 Plot [C2H5I] vs. time:
If a linear graph obtained  Zero Order Reaction

 Plot ln[C2H5I] vs. time:

If a linear graph obtained  First Order
Reaction
 Plot 1/[C2H5I] vs. time:
If a linear graph obtained  Second Order
Reaction
 12

Plot ln[N2O5] vs time:

 Linear graph
obtained
 The reaction is
ln [C2H5I]
12 Plot ln[N O ] vs time:
2 5
 Linear graph
obtained
ln [C2H5I]o k = – slope  The reaction is
= – (– 1.3 x 10–2 min–1) first order in N2O5
= 1.3 x 10–2 min–1

slope = – k

Time (min)
 Graph forlawZero
(a) From rate Order
of zero order : Reaction
(a) From Rate Law: Rate
Rate = k[A]0
Rate = k
[A]
(b) From Integrated Rate Law:
(i) [A]t = [A]o – kt (ii) [A]o – [A]t = kt
[A] [A]o – [A]
[A]o

t
 Graph for First Order Reaction
(a) From Rate Law:
Rate = k[A]

Rate

[A]
(b) From Integrated Rate Law:

[A] ln[A]t = ln[A]o - kt

(i) ln  kt (ii)
[A]t
ln[A]
[ A]
ln ln[A]o
[ A]

t t
 Graph for Second Order Reaction
(a) From Rate Law:

Rate = k[A]2
Rate Rate

[A] [A]2
(b) From Integrated Rate Law:

1 1 1 1
(i)  kt  (ii) [ A]  [A]  kt
[ A]t [A] t 

1
1 1
[ A] 
[ A] [A]

1
[ A]
time,t time,t
 Concentration-Time
Equation (Integrated
Order Rate Law Rate Law) Half-Life
[A]o
0 rate = k [A] = [A]o – kt t½ =
2k
[A]o
1 rate = k [A] ln = kt t½ = ln2
[A] k
1 1 1
2 rate = k [A] 2 = + kt t½ =
[A] [A]o k[A]o
 Zero order 1st order 2nd order
A  product A  product A  product
Rate= k[A]0 or Rate = k Rate = k [A]1 Rate = k [A]2
Unit k = M s-1 Unit k = s-1 Unit k = M-1 s-1
r r r

[A] [A] [A]

Integrated rate law Integrated rate law Integrated rate law
[A]0 – [A] = kt ln([A]0 / [A]) = kt 1/[A] – 1/[A]0 = kt

[A]
[A] [A] t1/2 = ln2/k
t1/2 = 1/k[A]0
t1/2 = [A]0/2k
[A]0

t t
t
ln[A] 1/[A]

ln[A]0
1/[A]0
t t
1.2 COLLISION THEORY

88
 LEARNING OUTCOME
SK025 1.2 (a)

 Explain Collision Theory

 Collision Theory
 The collision theory is based on these
ideas:
i) Molecules of reactants must collide in

order to form products.

ii) Products are formed only when effective

collisions occur between molecules.

 Effective Collision
 Effective collisions require the followings:
i) The colliding molecules must have

a total kinetic energy equal to or

greater than the activation energy, Ea.
ii) Collisions occur at the correct
orientation.
 LEARNING OUTCOME
SK025 1.2 (b)

 Define Activation Energy

 Activation Energy, Ea
 The activation energy, Ea is the minimum
energy
required to initiate a chemical reaction.
 The activation energy, Ea may be gained
through
the collisions of molecules.
 The energy is used to break the bonds between
atoms of the reactants
 Then these atoms will form new bonds in
the product.
 The Orientation of Collisions
 The correct orientation means that the collision of molecules occur
at the correct angle that favors the formation of products.
 Example:
2HI (g)  I2 (g) + H2 (g)



Effective Collision
 Reaction occurs


 Ineffective Collision
 No reaction occurs
 LEARNING OUTCOME
SK025 1.2 (c)

 Explain Transition State Theory

 Transition State Theory
 Explains the activation energy, Ea as the energy
required by reactant molecules to form the activated
complex.
 Activated complex is a temporary species formed by
the reactant molecules as a result of the collision before
they form the products.
 The transition theory is best explained by using the
energy profile diagram.
 13
CH3I + OH–  [I---CH3---O-H]  CH3OH + I–
Activation energy
H is needed to stretch
and deform bond in
I order to reach
transition state

H
H
Activated Complex H
 Activated
complex
(transition state)
Molecule bends,
Potential Energy C-I bond begins
to break

Ea C-OH bond forms

ΔH

Reaction Progress
 LEARNING OUTCOME
SK025 1.2 (d)

 Draw Energy Profile Diagram of a Reaction

Energy Profile Diagram
A + B C + D
Exothermic Reaction Endothermic Reaction

DHrxn= -ve DHrxn= +ve

 14
A key reaction in the upper atmosphere is
O3 (g) + O (g)  2O2 (g)
The Ea(fwd) is 19 kJ, and ΔHrxn for the reaction
is – 392 kJ.
Draw a reaction energy diagram and
calculate Ea(rev).
 14
O3 (g) + O (g)  2O2 (g)

Hrxn = Eafwd – Earev

–392 kJ = 19 kJ – Earev
Earev= 19 kJ+392 kJ
Ea rev
= 411 kJ = 411 kJ

Reaction Progress
1.3 FACTORS AFFECTING
REACTION RATE

103
 LEARNING OUTCOME
SK025 1.3 (a)

 Explain the effect of

 Concentration or Pressure
 Temperature
 Catalyst
 Particle Size on the Reaction Rate
Factors Affecting Reaction Rate
• CONCENTRATION / PRESSURE
1

• PARTICLE SIZE
2

• TEMPERATURE
3

• CATALYST
4
• CONCENTRATIONS OF REACTANTS:
Reaction rates generally increase as the
concentrations of the reactants are increased.

• TEMPERATURE:
Reaction rates generally increase rapidly as the
temperature is increased.

• CATALYSTS:
Catalysts speed up reactions.

• PARTICLE SIZE:
The rate increases as the smaller the size of reacting
particles.
 1. Concentration / Pressure
 Reactant concentration / Pressure of gases
PV = nRT
P = (n/V) RT  P = c R T
 pressure, p  concentration, c

Explanation:

P or c ,
- particles are closer to each other
- More likely to collide (higher collision frequency)
- Probability of effective collision increases
- More molecules with kinetic energy equal to or greater than Ea
- Reaction rate increases
 KEEP IN MIND
 Concentration change has
No effect on zero-order
reaction

Example: R Product
Rate law: r = k [R ]
Rate is independent of [R ]

108
 2. Particle Size

 The smaller the size of reacting particles, the larger the

contact surface area (solid reactant)
 Thus, frequency of collision increases
 Probability of effective collision also
increases
 Thus, the reaction rate increases.
 3. Temperature
 As temperature increases, kinetic energy of molecules
increases
 More collisions occur in a given time
 More molecules will have energy greater than activation
energy, Ea
 Effective collisions will increase
 Thus, the rate of reaction increases

110
 4. Catalyst
 A catalyst is a substance that increases the rate of a chemical
reaction without itself being consumed.
 A catalyst provides an alternative pathway which has a lower
activation energy compared to the one without catalyst.
 Addition of a catalyst increases the reaction rate by increasing
the frequency of effective collision. That is by
 Decreasing the Ea, and
 Correct orientation
 LEARNING OUTCOME
SK025 1.3 (b)

 Illustrate the effect of temperature on reaction rate

using Maxwell Boltzman Distibution Curve
 Effect of Temperature on Reaction Rate
 The effect of temperature on the reaction rate can be
explained in terms of kinetic theory.

Average Kinetic Energy ∝ Temperature

 The higher the temperature the higher the rate of reaction.
 Maxwell-Boltzmann distribution shows the kinetic energy
distributions for a reaction mixture at two different
temperature.
 -

Maxwell-Boltzmann Distribution Curve

Mole fraction Features:
 T 2 >T 1 : At T 2 , molecules that have
kinetic energy equal or greater than
Temperature: T2 > T1
activation energy is more compared to
T1 T1 .
T2
 The area under the curve equal to the
total number of molecules
 Number of molecules below both
curve are the same
 The shaded area represent number of
molecules possessing kinetic energy,
Ea Kinetic energy KE  activation energy, Ea
 Maxwell-Boltzmann Distribution Curve
Mole fraction Features:
 At higher temperature (T2),
 the peak of the curve moves to the
right
Temperature: T2 > T1
T1  the curves flattens
 more molecules with higher kinetic
T2 energy, KE (larger pink shaded
area)
 Very few molecules have low and high KE

Ea Kinetic energy
 Maxwell-Boltzmann Distribution Curve
Mole fraction  At higher temperature (T2)
 Particles absorb energy and
become more energetic
 More molecules posses kinetic
Temperature: T2 > T1
T1 energy equal to or higher than Ea
 i.e. higher frequency of effective
T2
collision
 Reaction rate at T2 increases

T ↑, average kinetic energy of the molecules ↑ ,

number of molecules with energy equal or
greater than Ea ↑ , effective collision ↑ , k ↑
Ea Kinetic energy
116
 LEARNING OUTCOME
SK025 1.3 (c)

 Compare the curve of the energy profile diagram

for a reaction with and without catalyst
 Effect of Catalyst
 Energy profile diagram showing the difference reaction in the
presence of catalyst and without catalyst.
Energy
Endothermic reaction

In the presence of catalyst, Ea is lower

Ea  More molecules have kinetic
(without) energy equal to or higher than Ea
Ea’(with)
 the probability of effective
ΔH collisions also increases
 thus, reaction rate increases.
Progress of reaction
 6

Characteristics of Catalyst
 They catalyze a specific reaction.
 Catalysts lower by the same amount the activation energies of
the forward and backward reactions of a reversible reaction.
 A catalyst neither alters the position of equilibrium nor
increases the yield of products.
 Do not change the value of H (enthalpy change) and K
(equilibrium constant) but change the K (rate constant) –
rate law @ arrhenius equation
 The catalyst may be changed physically but the mass of catalyst
is unchanged at the end of the reaction.
 It won’t be denaturalised at high temperature.
 LEARNING OUTCOME
SK025 1.3 (d)

 State Arrhenius Equation

 Arrhenius Equation
k : rate constant
k = Ae – Ea/RT R : universal gas constant
(8.314 Jmol–1 K–1 )
e : base of natural logarithm
T : absolute temperature (in K)
Ea : activation energy
Ea 1
ln k = ln A – A : frequency factor
R T
 LEARNING OUTCOME
SK025 1.3 (e)

 Explain the relationship between temperature

and activation energy to the rate constant based on
the Arrhenius Equation
 Temperature and Rate
Arrhenius equation k = Ae – Ea/RT

f : Fraction of molecular collisions

f = e – Ea/RT with energy greater or equal to Ea.

 Temperature affects the rate by affecting the rate constant (k)

 T  , average speed of particles  , frequency of collision 
 Only those collisions with enough energy to exceed Ea can lead to reaction
 Temperature rise enlarge fraction (f ) of collision with enough energy to
exceed Ea
 Arrhenius equation k = Ae – Ea/RT

f : Fraction of molecular collisions

f = e – Ea/RT with energy greater or equal to Ea.

 Magnitudes of both Ea and T affect the

fraction of sufficiently energetic collisions

• Higher T  larger k  increased rate

• Larger Ea  smaller k  decreased rate

 LEARNING OUTCOME
SK025 1.3 (f)

 Determine k, Ea, T and A using Arrhenius Equation

by calculation and graph
 Graphically Method
Ea 1
ln k = + ln A
R T
ln k
y = m x + c
ln A –
R must be 8.314 J mol–1 K–1
 Gradient, m = not 0.08206 atm L mol–1 K–1
because the unit of Ea
is in J or kJ !

()
 15
The rate constant for the decomposition of
nitrous oxide (N2O) into N2 molecule and O atom
has been measured at different temperatures:
k0.00187
(M -1s-1) T 600
(oC)
0.01130 650
0.05690 700
0.24400 750

Determine graphically the activation energy

for the reaction.
 15
k(M-1s-1) ln k T (oC) T (K) 1/T (K–1)

0.00187 – 6.281 600 873 1.15 x 10–3

0.01130 – 4.483 650 923 1.08 x 10–3

0.05690 – 2.866 700 973 1.03 x 10–3

0.24400 – 1.411 750 1023 0.98 x 10–3

 Plot graph: ln k versus 1/T
 15
ln k
Ea 1
ln k = ln A –
ln A R T
Slope = – Ea/R
= – 2.89 x 104 K

Ea = ( 8.314 J/K mol )( 2.89 x 104 K)

= 2.40 x 105 J/mol
Ea
slope = – = 240.2 kJ/mol
R

1/T (K–1)
 Calculation Method
KEEP IN MIND
– Ea/RT
Arrhenius equation k = Ae

Ea 1
ln k = + ln A
R T

Ea must be in J mol-1 R must be 8.314 J mol–1 K–1

T must be in Kelvin
 Ea 1
ln k = + ln A
R T
 If we know the rate constant at TWO different temperature:
1
ln k1 = ln A – Ea 1 ln k2 = ln A – Ea
R T1 R T2

k2 Ea 1 1
ln = – –
k1 R T2 T1
 16
The decomposition of N2O5 has an activation
energy of 103 kJ and a frequency factor of
4.3 x 1013 s–1. What is the rate constant for
this decomposition at
(a) 20 oC
(b) 100 oC
 16
Arrhenius equation k = Ae – Ea/RT

(a) A = 4.3 x 1013 s–1 T = 20 oC

Ea = 103 x 103 Jmol–1 = (20 + 273.15)K
= 293.15 K
R = 8.314 Jmol–1 K–1

103 x 103 Jmol–1

–
k = 4.3 x 1013 s–1 x e 8.314 Jmol–1 K–1 x 293.15 K

= 1.9 x 10–5 s–1

 16
Arrhenius equation k = Ae – Ea/RT

(b) A = 4.3 x 1013 s–1 T = 100 oC

Ea = 103 x 103 Jmol–1 = (100 + 273.15)K
= 373 K
R = 8.314 Jmol–1 K–1

103 x 103 Jmol–1

–
k = 4.3 x 1013 s–1 x e 8.314 Jmol–1 K–1 x 373.15 K

= 0.16 s–1
 17
The decomposition of HI has rate constants
k = 0.079 L mol–1 s–1 at 508oC
k = 0.24 L mol–1 s–1 at 540oC.
What is the activation energy of this reaction in
kJ mol–1?
 17
k2 Ea 1 1
ln = – –
k1 R T2 T1

k1 = 0.079 L mol–1 s–1 T1 = 508 oC

= (508 + 273.15)K = 781.15 K

k2 = 0.24 L mol–1 s–1 T2 = 540 oC

= (540 + 273.15)K = 813.15 K

Ea = ?
 17
k2 Ea 1 1
ln = – –
k1 R T2 T1

0.24 Lmol–1 s–1 Ea 1 1

ln = – –
0.079 Lmol s
–1 –1
8.314 Jmol K
–1 –1 813.15 K 781.15 K

Ea = 183311 J mol–1
= 183.3 kJ mol–1
 18
The rate constant of a first–order reaction is
4.60 x 10–4 s–1 at 350oC.
If the activation energy is 104 kJ/mol,
calculate the temperature at which its rate
constant is 8.80 x 10–4 s–1.
 18
k1 = 4.60 x 10–4 s–1 T1 = 350oC = (350 + 273.15)K
= 623.15 K
k2 = 8.80 x 10–4 s–1 T2 = ?

Ea = 104 x 103 J mol–1

k2 Ea 1 1
ln = – –
k1 R T2 T1
 18
k2 Ea 1 1
ln = – –
k1 R T2 T1

8.80 x 10–4 s–1 104 x 10 3

J mol–1 1 1
ln =– –
4.60 x 10 s
–4 –1
8.314 J mol–1 K–1 T2 623.15K
1 1
– = – 5.186 x 10–5
T2 623 K
1
= 1.553 x 10–3 K–1
T2
T2 = 643.8 K = 370.6oC
 END OF
SLIDE SHOW
 Edited By : Revised By :

ZAA MPJ
………………………. ……………………….

Approved By :

FU
……………………….