REACTION

KINETICS
7 hours

FNH

Chapter 10 : Reaction Kinetics

10.1
10.2
10.3

Reaction rate
Collision Theory
Factors Affecting
Reaction Rate

FNH

10 REACTION KINETICS
LECTURE 1

Learning Outcomes:
a) Define reaction rate
b) Explain the graph of concentration against
time in relation to reaction rate.
c) Write differential rate equation.
aA + bB cC + dD
Differential
rate 1equation:
1 d[A]
d[B]
1 d[C]
1 d[D]

rate = a dt
b dt
c dt
d dt
d) determine reaction rate based on differential
rate equation of a reaction.

REACTION KINETICS
Chemical kinetics is the study of the
rates of chemical reactions.
Important

industrial process
-Time
-Optimum yield
-Optimum conditions
*control over reaction,
*obtain products economically,
*using optimum conditions
4

10 .1 Reaction Rate
Reaction Rate (R)
The change in the concentration of
reactant or product with time (M/s)
General equation:

A
rate = (concentration)
t

d[A]
rate = - dt
d[B]
rate=+
dt

OR

B
The ve sign indicates [A]
decreases with time.
The +ve sign indicates [B]
increases with time.
5

Graph of concentration of reactant and product versus time

Concentration

Product

Reactant

Time
FNH

time
d[A]
rate = dt
d[B]
rate = +
dt

[B]

[A]
7

Reaction rate
The average rate is the rate over a period of time.
The rate of reaction at a given time (specified time) is
called an instantaneous rate of reaction.
The instantaneous rate at the beginning of a reaction
is called the initial rate of reaction.
Instantaneous rate is determined from a graph of
concentration vs time by drawing a line tangent to the
curve at that particular time (at the point concerned)

Rate of reaction
Reaction:
H2O2(aq) H2O(l) + O2(g)
Reaction rates are obtained
from the slopes of the straight
lines;
purple

blue

An average rate from the

purple line.
The instantaneous rate at
t =300 s from the red line.

red

The initial rate from the blue

line.
9

Br2 (aq) + HCOOH (aq)

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

instantaneous rate = rate at a specific time

[Br2]final [Br2]initial
d[Br2]
average rate = =dt
tfinal - tinitial

10

The differential rate equation

A differential rate equation enables the relationship
between the rate of disappearance of reactants and
the formation of products.
Simple example: aA

aB

1 d[A]
1 d[B]

Rate =
a dt
b dt
Where:
[ ] concentration of reactant or product (mol L -1)
t time (s @ min @ hr etc)
a and b are the stoichiometric coefficients

11

Consider the reaction,

aA + bB

Rate =

cC + dD

1 d[A]
1 d[B]
1 d[C]
1 d[D]

a dt
b dt
c dt
d dt

A, B, C and D represent subtances in (g) or (aq)

a, b, c and d are stochiomieric coefficients
12

The differential rate equation

Example:
The formation of NH3,
N2(g) + 3H2(g)

2NH3(g)

The differential rate equation is;

d[N 2 ]
1 d[H 2 ]
1 d[NH 3 ]

Rate =
dt
3 dt
2 dt
The equation means that the rate of disappearance
of N2 is 1/3 the rate of disappearance of H2 and 1/2
the rate of formation of NH3.
13

Example 1:
Consider the reaction, 2HI

H2 + I2,

determine the rate of disappearance of HI when

the rate of I2 formation is 1.8 x 10-6 M s-1.
Solution:

1 d[HI]
d[H 2 ]
d[I 2 ]

Rate =
2 dt
dt
dt
d[I 2 ]
= 1.8 10-6
dt
1 d[HI]
d[I 2 ]

Rate =
2 dt
dt

d[HI]
= -2 1.8 10-6 = - 3.6 10-6 M s-1
14
dt

NOTE:
d [HI] = - 3.6 10-6 M s-1

dt
-d[HI] = 3.6 10-6 M s-1
dt

Rate of disappearance oh HI is 3.6 10-6 M s-1

FNH

15

EXERCISE 1:
Write the rate expressions for the following reactions in terms of the disappearance of the reactants
and the appearance of the products:
(a) I- (aq) + OCl- (aq)
(b) 3O2 (g)

Cl- (aq) + OI- (aq)

2O3 (g)

(c) 4NH3 (g) + 5O2 (g)

4NO (g) + 6H2O (g)

16

EXERCISE 2:
Hydrogen gas produced nonpolluting product is
water vapour when react in O2 due to this reaction
has been used for fuel aboard the space shuttle,
and may be used by Earth-bound engines in the
near future.
2H2(g) + O2(g)
2H2O(g)
Express the rate in terms of changes in [H2],
[O2] and [H2O] with time.
When [O2] is decreasing at 0.23 mol L-1 s-1,at
what rate is [H2O] increasing?

(0.46 mol L-1 s-1)

17

Exercise 3:
Consider the reaction,
2NO(g) + O2(g)

2NO2(g).
Suppose that at a particular time during the
reaction nitric oxide (NO) is reacting at the rate of
0.066 Ms-1
a) At what rate is NO2 being formed?
b) At what rate is molecular oxygen reacting?

18

Exercise 4:
Consider the reaction,
N2(g) + 3H2(g)

2NH3(g)

Suppose that at a particular moment during the

reaction molecular hydrogen is reacting at the rate
of 0.074 M s-1
a) At what rate is ammonia being formed?
b) At what rate is molecular nitrogen reacting?
19

Lecture 2
Learning Outcomes:

e) Define
i. rate law.
ii. Order of reaction.
f)

Write rate law with respect to order of reaction

h) Determine the order of reaction involving a

single reactant using
i. initial rate method
ii. the units of rate constants, k
20

The Rate Law (Rate equation)

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.
aA + bB
cC + dD

Rate [reactant]

Rate = k [A]x[B]y
k is called rate constant
x and y is called order of reaction

NOTE!
The values of x and y can only be determined
experimentally not from the stoichiometry of the
balance
chemical equation
FNH
21
21

ORDER OF REACTION
Order of reaction is defined as the power to
which the concentration of a reactant is raised in
the rate equation.
The order of a reactant is not related to the stoichiometric
coefficients of the reactants in the balanced chemical
equation. It can be only determined experimentally

Rate = k [A]x[B]y
Order of reaction with respect to A is x
Order of reaction with respect to B is y
The exponents x, y, can be integers,
fractions or decimal or negative values.

Overall order of reaction = (x + y)

22

Example
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]

Solution:
The reaction order respect to NO : 2
The reaction order respect to O2 : 1
Overall reaction order: 2 + 1 = 3
23

(b) CH3CHO (g)

CH4(g) + CO(g);

rate = k[CH3CHO]3/2
Solution:
The order of reaction with respect to CH3CHO :
3/2
: 3/2
+
(c) The
H2O2overall
(aq) + 3Iorder
(aq) + of
2Hreaction
(aq)
I3-(aq) + 2H2O(l);
rate = k[H2O2][I-]
Solution:
The order of reaction with respect to H2O2 : 1
The order of reaction with respect to I- : 1
The order of reaction with respect to H+ : 0
overall order of reaction: 1+1= 2

24

NH

The order of reaction

Order of Reaction
Zero Order

First Order

Second Order

25

Determining the Order of Reaction

There are 5 method to determine the order
of reaction:
1.Using rate law
2.Using the unit of the rate constant.
3.Using initial rate mwethod
4.Using half-life method (concentration vs
time graph)
5.Using linear graph method
26

1. Determining the order of

reaction from rate law
For reaction

Products

Rate = k [A]x
i) If x = 0
Rate = k [A]0
Rate = k
Rate is not dependent on [A]

Therefore this reaction is zero order with respect to

27

ii) If x= 1
Rate = k [A]1
Assume [A]i = 1.0M,
Rate1 = k (1.0M)
If the [A] is doubled from 1.0M to 2.0M,
Rate2 = k (2.0M)
= 2k(1.0M)
Rate2 = 2 Rate1
Doubling the [A] will double the rate of reaction.

Therefore this reaction is first order with respect to A

28

iii) If x = 2
Rate = k[A]2
Assume [A]i = 1.0 M,
Rate1 = k (1.0 M)2
If the [A] is doubled from 1.0 M to 2.0 M,
Rate2 = k (2.0 M)2
= 4k(1.0 M)
Rate2 = 4 Rate1

Doubling [A], the rate will increase by a factor of 4 (by fou

Therefore the reaction is second order with respect

29

2.The
Determining
therate
order of
units of
reactionconstant,
from unit ofkrate constant
A

Products

Rate, r = k [A]x
i) zero order
Rate = k [A]0
Rate = k
unit k =unit rate
= mol L-1 s-1 or Ms-1
30

ii) First order

Rate = k [A]1

k=

Unit k =

rate
[A]
M s-1
M

= s-1
iii) Second order

Rate = k [A]2
k=

rate
[A]2

M s-1
Unit k =
M2

= M-1 s-1
31

The rate equation, order of reaction and unit of k for

general equation: A + B
C show in table below:The rate
equation
R=k[A]0[B]0
R=k
R=k[A]1
R=k[B]1
R=k[A]1[B]1
R=k[A]2
R=k[B]2
R=k[A]2[B]1

Order of
reaction
0

Unit of k

s-1

M-1s-1

M-2s-1

Ms-1

Note :
Reaction order is always defined in term
reactant
(not product) concentrations

32

Example :

S2O82- + 3I-

2SO42- + I3-

The above reaction is first order with respect to iodide io

and to thiosulphate ions.
a) Write the rate of equation for the reaction.
b) What is the unit of rate constant, k?
Solution :
a) Rate = k [S2O82-]1[I-]1
b) Rate = k [S2O82-]1[I-]1
rate
k=
[S2O82-]1[I-]1

Unit k =

Ms-1
M2

= M-1 s-1
33

3. Determination of the orders of

reaction rate using initial rate
method
EXAMPLE:
O2(g) + 2NO(g)
Experiment

Initial Reactant
Concentrations (molL-1)
O2

NO

2NO2(g)
Initial Rate
(M s-1)

1.10x10-2

1.30x10-2

3.21x10-3

2.20x10-2

1.30x10-2

6.40x10-3

1.10x10-2

2.60x10-2

12.8x10-3

3.30x10-2

1.30x10-2

9.60x10-3

1.10x10-2

3.90x10-2

28.8x10-3
34

Solution:
O2(g) + 2NO(g)

2NO2(g)

rate = k [O2]m[NO]n
Compare 2 experiments in which the concentration of one
reactant varies and the concentration of the other
reactant(s) remains constant.

rate2
rate1 =

k [O2]2m[NO]2n
k [O2]1m[NO]1n

6.40x10-3Ms-1
3.21x10-3Ms-1

[O2]2m
[O2]1m

2.20x10-2mol/L

[O2]2
[O2]1

1.10x10-2mol/L

2 = 2
,m=1
The reaction is first order with respect to O2
m

Do a similar calculation for the other reactant (s).

35

To find the order with respect to NO, we

compare experiment 3 and 1, in which [O2] is
held constant and [NO] is doubled:
n
m
n
k
[O
]
[NO]
[NO]
Rate 3
2 3
3
3
=
=
[NO]1
Rate 1
k [O2]1m [NO]1n
n
-3
-1
12.8 x 10 Ms
2.60 x 10-2mol/L
=
-3
-1
3.21 x 10 Ms
1.30 x 10-2mol/L
4 = 2n ; n = 2
The reaction is second order with respect to NO
Thus the rate law is :
Rate = k[O2][NO]2
36

Exercise 1:

ClO2(aq) + 2OH- (aq) products

The results of the kinetic studies are given below.
exp

[ClO2]
M

[OH-]
M

Initial rate,
Ms-1

0.0421

0.0185

8.21 1 0-3

0.0522

0.0185

1.26 1 0-2

0.0421

0.0285

1.26 1 0-2

a) Explain what is meant by the order of reaction.

b) Referring to the data determine
(i) rate law /rate equation
(ii) rate constant, k
(iii) the reaction rate if the concentration of both ClO 2
and OH- = 0.05 M

37

Exercise 2:
Write rate law for this equation,
A + B

i)

When [A] is doubled, rate also doubles. But

doubling the [B] has no effect on rate.
ii) When [A] is increased 3x, rate increases 3x,
and increasing of [B] 3x causes the rate to
increase 9x.
iii) Reducing [A] by half has no effect on the rate,
but reducing [B] by half causes the rate to be
half the value of the initial rate.
38

Exercise 3:
Many gaseous reactions occur in a car engine and exhaust
system. One of the gas reaction is given below.
NO2(g) + CO(g)
NO(g) + CO2(g)
Rate = k [NO2]m[CO]n
Use the following data to determine the individual and overall reaction orders:
Experiment

Initial Rate(Ms-1)

Initial [NO2](M)

Initial [CO](M)

0.0050

0.10

0.10

0.080

0.40

0.10

0.0050

0.10

0.20

39

LECTURE 3

Integrated Rate Law and Half life

Learning Outcomes:
g)Write the integrated rate equation for zero, first
and second order reactions.
h)iii) To define half-life,t1/2
i) Perform calculation using the integrated rate
equations.

40

Integrated rate equations

Is used to derive the rate law for zero order, first order and
second order reaction.
Integrated Rate Law of a Zero Order Reaction
A zero order reaction is a reaction independent of the
concentration of reactant.
A product

rate

The rate law is given by

rate = k[A]0
rate = k
[A] M

41

-d[A] = k
dt
- d[A] = kdt .(1) intergrating equation (1)
- d [A] = k dt
- [A] = kt + c
substituting t=0, [A] = [A]0
- [A]0 = k(0)+c
c = - [A]0
[A]0 -[A] = kt
Unit of k for zero order reaction M s-1
42

Graphs for zero order reaction

M
[A]o [A]

[A]o [A] = kt

k= rate constant can

be determined from
the slope of the
straight line

y = mx + c

t
[A]
[A]o

rate

[A] = -k t + [A]o
y=m x+c

[A]

43

Half-life (t)
Half life (t) is the time required for the
concentration of a reactant to decrease to
half of its initial value.

44

Half life of a zero order reaction

Substituting t = t1/2 , and [A] = [A]0 into the zero
order reaction, gives
2
[A]0 - [A] = kt
[A]0 [A]0 = kt1/2
2
Solving for t1/2 gives
t1/2 = [A]0
2k

45

Intergrated Rate Law of a First Order

Reactions
A first order reaction is a reaction whereby its rate
depends on the concentration of reactant raised to the
y = mx + c
first power.
Consider the reaction :
A

Rate
Ms-1

products

From the rate law,

rate = k[A]

[A] ,M

46

For first order reaction,

Rate = k[A]
- d[A]
dt

- d[A]
[A]

- d[A]

[A]

= k dt

k[A]

substituting
t = 0, [A]=[A]0

k dt

- ln [A] = kt + c

- ln [A]0 = k(0) + c
c = ln[A]0
-ln [A] = kt ln[A]0
ln [A]0 = kt
[A]

47

Characteristic graphs of 1st order reaction

ln[A]o ln[A] =kt

[A]

ln[A]

ln[A] = - kt +ln[A]o
[A]0
ln -----[A]

kt

ln[A]o
[A]

ln[A]o

t
48

Example 1:
The reaction 2A
B is first order with respect A with a
rate constant of 2.8 x 10-2 s-1 at 800C. How long will it take
for A to decrease from 0.88 M to 0.14 M ?
[A]0 = 0.88 M
ln[A]o ln[A] = kt
[A] = 0.14
M
kt = ln[A]0 ln[A]
[A]0
0.88 M
ln
ln
[A]
0.14 M
ln[A]0 ln[A]
=
= 66 s
t=
=
-2
-1
k
k
2.8 x 10 s

49

Example 2:
Decomposition of H2O2 (aq) is first order, given that k = 3.66
x 10-3 s-1 and [H2O2 ]o = 0.882 M, determine:
a) the time at which [H2O2] = 0.600 M
b) the [H2O2 ] after 225 s.
Solution :
a)
ln

[H2O2]0

[H2O2]
ln 0.882
0.600

= kt
= 3.66 x 10-3 s-1 x t

50

ln 1.47 = 3.66 x 10-3 s-1 x t

ln 1.47
t=
3.66 x 10-3
= 105.26 s
b)

[H2O2]0
ln
= kt
[H2O2]
ln 0.882 = 3.66 x 10-3s-1x 225 s
[H2O2]
[H2O2] = 0.387 M
51

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 500C.
CH2
CH2

CH2

CH3-CH=CH2

a) If the initial concentration of cyclopropane was 0.25 M, what is the

concentration after 8.8 minute. (0.18 M)
b) How long will it take for the concentration of cyclopropane to
decrease from 0.25 M to 0.15 M? (13 min)
c) How long will it take to convert 74 percent of the starting material?
(33 min)

52

Half-life of a first-order reaction

The half-life, t, is the time required for the concentration of a
reactant to decrease to half of its initial concentration.
t=t when [A] = [A]0
2
[A]0
ln
[A]0/2
ln2
0.693
t =
=
=
k
k
k
t = ln 2
k

53

EXAMPLE 1:
What is the half-life of N2O5 if it decomposes with a
rate constant of 5.7 x 10-4 s-1?
0.693
t = ln2 =
= 1200 s = 20 minutes
-4 -1
k
5.7 x 10 s

How do you know decomposition is first order?

units of k (s-1)

54

Example 2:
The decomposition of ethane C2H6 to methyl radicals is a
first order reaction with a rate constant of 5.36 x 10 -4 s-1 at
700o C.
C2H6 (g)
2 CH3 (g)
Calculate the half life of the reaction in minutes.
Solution:
t1/2

=
=

ln 2
k
0.693
5.36 x 10-4

= 1.29 x 103 s
= 21.5 min

55

Problem 1
What is the half-life of a compound if 75% of a given
sample of the compound decomposes in 60 min?
Assume it is first-order reactions kinetics.
(t1/2=30 min)
Problem 2
The decomposition of SO2Cl2 is a first-order reaction.
SO2Cl2(g)
SO2 (g) + Cl2 (g)
i) Write the rate differential equation for the reaction.
ii) Calculate the value of rate constant, k at 500 K if
5.00 % SO2Cl2 decomposed in 6.75 min.
Ans (7.6X10-3)
iii) Specify the half-life for the decomposition reaction.

56

Integrated rate law of a Second Order

Reactions
A second order reaction is a reaction which rate
depends on the concentration of one reactant
raised to the second power or on the concentration
of two different reactants each raised to the first
power.
Example
A product
Where
d[A]
Rate = dt

= k[A]2
57

Rearrange to:d[A]
[A]2

= kdt (1)

Integrating equation 1
1 = kt + c (2)
[A]
At t =0, [A] = [A]o
1 = k(0) + c
[A]0
c = 1 (3)
[A]0

Combining (3) and (2)

and rearranging the
results gives:
1 = - 1 + kt
[A]
[A]0

58

Characteristic graphs for second order

reaction
rate

[A]
rate

[A]2
59

Graphs for second order reaction

1
1
+ kt
=
[A]o
[A]

[A]

t
1/[A] 1/[A]o

1/[A] M-1

1/[A]o
t
FNH

t
60

Half life of a second order reaction

1
=
[A]

1
+ kt
[A]0

[A]= [A]o
Substituting t = t1/2
2
1
1
+ kt1/2
=
[A]0
[A]0
2
t1/2=

1
k[A]0
61

Example 1:
Iodine atoms combine to form molecular iodine in
the gaseous phase
I (g) + I (g) I2(g)
This reaction is a second order reaction , with the
rate constant of 7.0 x 109 M-1 s-1
If the initial concentration of iodine was 0.086 M,
i)
calculate its concentration after 2 min.
ii)
calculate the half life of the reaction if the
initial concentration of iodine is 0.06 M and
0.42 M respectively.
62

Solution :
i)

ii)

1
1
+ kt
=
[A]
[A]0
1
1
9
+
(7.0
x
10
x 2 x 60 )
=
[A]
[0.086]
= 8.4 x 1011
[A] = 1.190 x 10-12 M
[I2] = 0.06 M
1
1
=
t1/2=
9
k[A]0 7.0 x 10 x 0.060
= 2.4 x 10-10 s
63

[I2] = 0.42 M
t1/2=
=

1
k[A]0
1
7.0 x 109 x 0.42

= 3.4 x 10-10 s

64

Lecture 4
Objective:
h) Determine the order of reaction
involving a single reactant using:
iii) half-life based on the graph of
concentration against time.
iv) linear graph method based on the
integrated rate equation and rate law.

65

4. Determination of the orders of

reaction rate using half life
method
PlotSketch a [A] vs t graph
Zero order:
[A]
t1/2 = [A]0
2k

t
FNH

*A linear graph
66

First order:
[A]o

t = ln 2
k

[A]o/2
[A]o/4
[A]o/8

*Half-life is constant!
FNH

67

Second order:
[A]0

t1/2=

[A]0/2

1
k[A]0

[A]0/4
[A]0/8

2x

4x

*Half-life is twice the initial half-life.

68

Example 1:
First-order reaction
A

product

No. of
half-lives

[A]o = 8 M

1/2
t = ln2
k

Example 2:
The following results were obtained from an
experimental investigation on dissociation of
dinitrogen pentoxide at 45oC
N2O5(g) 2 NO2(g) + O2(g)
time, t/min

10

20

30

40

50

60

[N2O5] x 10-4 M

176

124

93

71

53

39

29

Plot graph of [N2O5] vs time, determine

i) The order of the reaction
ii) the rate constant k

70

Solution :
180
160
140
120

[N2O5] x 100
10-4 /M 80
60
40
20
10

20

30

40 50 60 70

80

Time ( min)
71

i) Based on the above graph,

Time taken for concentration of N2O5 to change
from 176 x 10-4 M to 88 x 10-4 M is 20 min
Time taken for concentration of N2O5 to change
from 88 x 10-4 M to 44 x 10-4 M is also 20 min
The half life for the reaction is a constant and
does not depend on the initial concentration of
N2O5.
Thus, the above reaction is first order
ln2

ii) k =
= 0.03 min-1
20 min

72

5. Determination of the orders of

reaction rate using linear graph
method
Zero Order:
A plot of [A] vs t should be linear
[A]
[A]0

73

First Order:
A plot of ln [A] vs t should be linear
ln[A]
ln[A]0

74

Second Order:
A plot of 1/ [A] vs t should be linear

1/[A]

1/[A]0
t
75

Example:
The following data were obtained from the gas-phase
decomposition of hydrogen iodide:
Time (h)

[HI] (M)

1.00

0.50

0.33

0.25

Find the order of HI?

Solution:
Strategy; prepare a table listing [HI], ln [HI] and 1/[HI]
Time (h)

[HI]

Ln [HI]

1/[HI]

1.00

1.00

0.50

-0.69

2.00

0.33

-1.10

3.00

0.25

-1.39

4.00

76

 Then, sketch graphs:

ln[HI]

[HI]

1/[HI]

Because a plot of 1/[HI] vs t is linear, the decomposition of HI

must be a second order.

77

Summary of the Kinetics of Zero-Order, First-Order

and Second-Order Reactions

Order
0

Concentration-Time
Equation

Rate Law

[A] = [A]0 - kt

rate = k

rate = k [A]

ln[A] = ln[A]0 - kt

rate = k [A]

1
1
=
+ kt
[A]
[A]0

Half-Life
t =

[A]0
2k

t = ln2
k
1
t =
k[A]0

78

Zero order
A product
r = k [A]0
Unit k = M s-1

1st order
A product
r = k [A]1
Unit k = s-1
r

r
[A]

[A]

Integrated rate law

[A]0

t1/2 = [A]0/2k

[A]2

Integrated rate law

ln([A]0 / [A]) = kt

1/[A] 1/[A]0 = kt

ln[A]

[A]

[A]

Integrated rate law

[A]0 [A] = kt
[A]

2nd order
A product
r = k [A]2
Unit k = M-1 s-1

[A]

1/[A]

ln[A]0
1/[A]0

[A]0 - [A]

ln([A]0 / [A])

t1/2 = ln2/k

t
1/[A] 1/[A]0

t1/2 = 1/k[A]0
79

Exercise
The data refers to the decomposition of
N2O4 at 100kPa and 380K
[N2O4]/M

0.6

0.9

1.2

Initial rate/Ms-1

3.2x10-3

4.8x10-3

6.4x10-3

a)Determine the order with respect to N 2O4

b) Calculate half life of the reaction.
c) Calculate the initial rate if the initial
concentration of N2O4 is
i) 1.5x103M
ii) 3.1x10-2M

80

Collision theory and

transition state
LECTURE 5
Objectives:
1. Explain collision theory
2. Define activation energy.
3. Explain transition state theory
4. Draw energy profile diagram of a reaction

81

Collision Theory

Collision Theory is the theory to explain the rate of

chemical reactions. It is based on:1- molecule must collide to react
2- molecules must possess a certain minimum kinetic energy
(activation energy) to initiate the chemical reaction.
3- molecule must collide in the right orientation in order for
the reaction to occur.
Number of effective collisions
Rate
time
According to this theory, not all collisions between the
molecules result in the formation of products.
82

Only effective collisions cause formation of

product;
- collisions of molecules with Ea and
- at correct orientation.

The activation energy (Ea) is the minimum

energy that must be supplied or required by
collisions for a reaction to occur.

83

Definition of Activation Energy (Ea)

Activation energy
is the minimum
energy required to
initiate the
chemical reaction.

84

Importance of Orientation

Orientation is unimportant

Orientation is important
85

Importance of Orientation

Orientation is important

86

Transition State Theory

The configuration of the atoms of the colliding
species at the time of the collision is called the
transition state.
Species formed at transition state is called activated
complex.
Activated complex- the species temporarily form by
the reactant molecule as the result of the collision
before they form product. (also called the transition
state)
87

Characteristics of Activated Complex

Very unstable i.e.

Its potential energy is greater than reactants or

products.

The activated complex and the reactants are in

chemical equilibrium.

It decomposes to form products or reactants.

88

Energy Profile Diagram: Exothermic reaction

Potential energy
Activated complex

Ea
Reactant

A reaction profile shows

potential energy plotted as a
function of the progress of the
reaction.
*The difference in potential
energies between the products
and the reactants is -H for the
reaction.

*Reactant molecules must

have
enough
energy
to
product
overcome an energy barrier
separating
products
from
Progress of reaction
reactants, Ea.
89

Energy Profile Diagram: Exothermic reaction

Activated complex
Transition state
Ea (Forward reaction)
Ea (reverse reaction)

FNH

CO(g) + NO2(g)

CO2(g) + NO(g)

90

Energy Profile Diagram: Endothermic reaction

activated complex.
Ea
(reverse reaction)
Ea
(forward reaction)

Product
H
Reactant
91

Energy Profile Diagram: Endothermic reaction

Ea
H

2NOCl

2NO + Cl2

92

NOTE: Ea for reverse reaction

EXOTHERMIC
Ea(reverse) = Ea(forward) + H

ENDOTHERMIC
Ea(reverse) = Ea(forward) - H
FNH

93

Energy profile diagram and activation energy for :

a)Exothermic reaction

b) Endothermic reaction

94

Example:
1. For the reaction A + B
C + D , the enthalphy change of
the forward reaction is + 21 kJ/mol. The activation energy of the
forward reaction is 84 kJ/mol.
a) What is activation energy of the reverse reaction?
b) Sketch the reaction profile of this reaction
2. Draw a potential energy diagram for an exorthermic reaction.
Indicate on the drawing:
a) Potential energy of the reactants and the products
b) The activation energy for the forward and the reverse
reaction
c) The heat of the reaction

95

Factors affecting rate of

reaction
LECTURE 6

96 96

Objective:
To explain the effect of the following factors on the
reaction rate.
Concentration or pressure
Temperature
Catalyst
Particle size
Explain the effect of temperature on reaction rate
using Maxwell-Boltzman distribution
Explain the effect of catalyst on activation energy
based on energy profile diagram.

97

Factors affecting rate of reaction

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.

PRESSURE

PARTICLE SIZE:
The rate increases as the smaller the size of
reacting particles .
98

A) CONCENTRATIONS OF REACTANTS
Reaction rate

collision
time

The frequency of collision increases with the

concentration
4 particle system
(2 and 2) 4 collision

99

A) CONCENTRATIONS OF REACTANTS
A concentration of reactants increases, the frequency
of collision increases.
This would also result in the increase in the quantity of
effective collision. Thus the reaction rate increases.
5 particle system
(3 and 2) 6 collision

100

A) CONCENTRATIONS OF REACTANTS
This observation correlates with the RATE LAW that has
been previously discussed
x

Reaction rate = k [ A ] [ B ]
(A & B = reactants)
(x & y = rate order)

Based on this equation,

Reaction rate concentration of reactants
(depending on its rate order)
REMINDER!
Only in zero order reactions, the rate of reaction is not
dependant upon the concentration of the reactants.
Reaction rate = k [ A ]0 = k (constant)

101

Pressure
When pressure is applied, volume
decreases. Number of molecules per unit
volume increases resulting in more
collisions per second.
Number of effective collision increases so
the rate of reaction also increases.

102

B) TEMPERATURE

As temperature increases, kinetic energy, of

molecules increases
So, more collisions occur in a given time
Furthermore, the higher the kinetic energy, the
higher the energy of the effective collisions.
So more molecules will have energy greater
than activation energy, Ea
Thus, the rate of reaction increases
103

Distribution of Kinetic Energies of Molecules

Represent total number of molecules

with kinetic energy greater than104Ea

 The area under curve represent the total

number of molecules in the reaction
So that ,the area under each curve ( T1
and T2 ) is the same, because the total
number of molecules used for temperature
T1 and T2 are the same.

105

 At higher temperature the average energy

increases, the fraction of molecules with
energy higher than Ea will increases also.
The shaded area under the curve
represent the number of molecules with
kinetic energy greater than the activation
energy

106

 The graph for T1 shows that only a small

fraction of molecules has sufficient energy
( the Ea) to react at T1.
At the higher temperature T2, the fraction of
molecules that have sufficient energy( equal
to or greater than Ea) to react increases.
So that rate of reaction will increases with
increasing of temperature

107

C) CATALYST

A catalyst is a substance that increases the rate

of a chemical reaction without itself being
consumed.
Addition of a catalyst increases the reaction rate
by increasing the frequency of effective collision.
That is by
Decreasing the Ea, and
Correct orientation

FNH

108

Function of catalyst:
To speed up the reaction rate by providing an alternative
pathway by lowering the activation energy.

109

 Addition of a catalyst changes the value of k (rate

constant) .
x

Reaction rate = k [ A ] [ B ]

(A & B = reactants)
(x & y = rate order)

The catalyst reacts by reducing the Ea and increasing

A, thus increasing the k.

Ea 1
ln k
( ) ln A
R T
FNH

110

 When Ea decreases, k increases,

REACTION RATE increases

rateuncatalyzed < ratecatalyzed

uncatalyzed

catalyzed

Ea > Ea

111

Ea (without catalyst)

Reaction pathway

112

D) PARTICLE SIZE

The smaller the size of reacting particles,

the greater the total surface area exposed
for reaction .
The greater surface area causes a greater
frequency of collisions,thus increasing the
reaction rate.

113

Arrhenius equation
LECTURE 7

114

Objective:
a) State Arrhenius equation.
b) Relate temperature and activation energy to the
rate constant based on the Arrhenius equation.
c) Determine k, Ea, T and A using Arrhenius
equation by calculation and graphical method.

115

ARRHENIUS EQUATION
In 1889, Svante Arrhenius proposed the following
mathematical expression for the effect of
temperature on the rate constant, k:
-Ea

k = Ae

RT

Where
k = rate constant
A = constant known as the collision frequency factor
e = natural log exponent
Ea = activation energy for the reaction
R = universal gas constant (8.314 J mol-1 K-1)
116
T = absolute temperature(in Kelvin)

ARRHENIUS EQUATION
The relation ship between the rate constant, k and
temperature can be seen in the k vs T graph:

-Ea

k = Ae

FNH

RT

T (K)

117

ARRHENIUS EQUATION DERIVATION

The relationship between k and T is clearer when
we further derive the Arrhenius Equation

k Ae
Natural log both ends

Ea

ln k ln( A.e

RT

Ea

RT

ln k ln A ln(e
ln k
Thus
See the linear relationship?

Ea

Ea
ln e ln A
RT

Ea 1
ln k
( ) ln A
R T
y = m x+ C

RT

)
(But ln e = 1)

118

Graph Representation Of The Arrhenius Equation

Plotting a ln k vs 1/T graph would show a clearer
relationship between k (Rate constant) and temperature

Ea 1
ln k
( ) ln A
R T
Where,
Ea = Activation Energy
R = 8.314 Jmol-1K-1
T = Absolute Temp
A = Collision freq. factor

A plot of In k versus 1/T

gives a straight line with
slope m is equal to Ea/R
and whose intersect c
with the y axis is In A

119

 If the value of A (collision frequency factor) is not

known and the same reaction conducted at two
different temperatures.The Arrhenius equation at each
temperature can be written and combined to formed
the equation shown in the box.
Ea 1
ln k1
( ) ln A
R T1

and

ln k 2

Ea 1
( ) ln A
R T2

Rearranging the equations would give

Ea 1
ln k1
( ) ln A
R T1
Since A is a constant
E 1
E
1
ln k1 a ( ) ln k 2 a ( )
R T1
R T2

Ea 1
Ea 1
ln k1 ln k2
( )
( )
R T2
R T1

Ea 1
ln k 2
( ) ln A
R T2

k1 Ea 1 1
ln
( )
k2
R T2 T1
120

Exercise: the Activation energy

The decomposition of hydrogen iodide,

2 HI (g) H2(g) + I2(g)

has rate constants of 9.51 x 10-9 L mol-1 s-1 at 500 K and
1.10x10-5 L mol-1 s-1 at 600 K. Find Ea.
DATA:

k1 = 9.51 x 10-9 L mol-1 s-1

k2 = 1.10 x 10-5 L mol-1 s-1

T1 = 500K
T2 = 600K

SOLUTION:

k1 Ea 1 1
ln
( )
k2
R T2 T1

k1 1 1 1
Ea R ln( )( )
k 2 T2 T1

9.51 10 9 1
1 1
Ea (8.314) ln(
)(

)
5
1.10 10
600 500
Ea = 1.76 x 105 J/mol = 176 kJ/mol
121

Example 1:
The rate constants for decomposition of acetaldehyde
2HI(g)

H 2(g) + I2(g)

were measured at five different temperatures. The data are

shown below. Plot ln k versus 1/T, and determine
the activation energy (in kJ/mole) for the reaction.
k (1/M s)

T (oC)

3.52 x 10-7

283

3.02 x 10-5

356

2.19 x 10-4

393

1.16 x 10-3

427

3.95 x 10-2

508

122

Solution
We need to plot ln k (on the y-axis) versus 1/T( on
the x-axis). From the given data we obtain
ln k

1/T (K-1)

14.860

1.80 x 10-3

10.408

1.59 x 10-3

8.426

1.50 x 10-3

6.759

1.43 x 10-3

3.231

1.28 x 10-3

123

ln k
-2
-4
-6
-8

-10
-12
-14

-16
x 10-3

1/T(K-1)

Plot of ln k versus 1/T. The slope of the line

is calculated from two pairs of coordinates.
124

Slope =

(-14.0) (-3.9)
(1.75 1.3) x 10-3 K-1
= -2.24 x 104 K

The slope, m = Ea/R.

Ea = R (m)
= (8.314 J K-1 mol-1) x
( 2.24 x 104 K)
= 1.9 x 105 J mol-1
= 190 kJ mol-1
125

 An equation relating the rate constants k1 and k2

at temperatures T1 and T2 can be used to
calculate the activation energy or to find the rate
constant at another temperature if the activation
energy is known.
ln k1 = ln A Ea/RT1
ln k2 = ln A Ea/RT2
Subtracting ln k2 from ln k1 gives
ln k1 ln k2 = Ea/R (1/T2 1/T1)

ln k1/ k2 = Ea/R (1/T2 - 1/T1 )

126

Example 10.7.2:

The rate constant of a first-order reaction is

3.46 x 10-2s-1 at 298 K. What is the rate
constant at 350 K if the activation energy
for the reaction is 50.2 kJ/mole?
Solution
Given
k1 = 3.46 x 10-2 s-1 k2 = ?
T1 = 298 K
T2 = 350 K
Subtituting in equation
ln k1/ k2 = Ea/R (1/T2 1/T1)
127

ln 3.46 x 10-2 = 50.2 x 103 J/mol

k2
8.314 J/K mol

298K 350K
(298K)(350K)

Solving the equation gives

ln 3.46 x 10 -2 = 3.01
k2
3.46 x 10 -2 = 0.0493
k2
k2

= 0.702 s 1

128

Changes in
condition

Reaction rate

Rate constant

Increase in
temperature

Increase

Increase

Decrease in
temperature

Decrease

Decrease

Addition of catalyst Increase

Increase

Increase in
pressure

Increase

No effect

Decrease in
pressure

Decrease

No effect

Increase
concentration

Increase

No effect

Decrease
concentration

Decrease

No effect

129