1.

1: REACTION RATE

CHAPTER 1.0
1.2: COLLISION THEORY
REACTION
KINETICS
1.3: FACTORS AFFECTING
REACTION RATE
 COURSE LEARNING OUTCOMES
CLO OUTCOMES
1 Explain basic concepts and principles of physical chemistry in novel and
real life situations.
C2, PLO1, MQF LOD 1
Teaching & Learning Strategy : LECTURE

2 Demonstrate the correct techniques in handling laboratory apparatus

and chemicals when carrying out experiments.
P4, PLO2, MQF LOD 2
Teaching & Learning Strategy : PRACTICAL, DEMONSTRATION

3 Solve chemistry related problems by applying basic concepts and

principle in physical chemistry.
C4, PLO4, CTPS3, MQF LOD 6
Teaching & Learning Strategy : TUTORIAL

2
 CHEMISTRY
SK025
MODE : LECTURE (CLO 1)

Student Learning Time (SLT) for lecture :

Non Face-to-face Face-to-face

(Preparation) (During Class)
1.5 hour 1.5 hour

3
Assessment of learning outcomes :

CLO T&L Strategy Assessment

1 Lecture Final Examination
(paper 1)
2 Practical Practical Test
Demonstration
3 Tutorial Assignment
Final Examination
(paper 2)

4
 TEACHING LEARNING OUTCOMES
(WEEK 1, 1st HOUR)

At the end of the lesson, student should be able to :

1.1: REACTION RATE

a) Define reaction rate.

b) Write differential rate equation.

d) Define rate law, order of reaction and half-life.

e) Write rate law with respect to the order of rection.

f) Write the integrated rate equation for zero, first and second order
reactions.

5
 REACTION KINETICS

1.1 Reaction Rate

CHEMISTRY UNIT 6
KOLEJ MATRIKULASI JOHOR
 REACTION RATE
 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 ] 
7
 UNIT OF REACTION RATE

A B
D[A] D[B]
rate = – Dt rate =+
Dt

The negative sign indicates concentration of A decreases with time.

The positive sign indicates concentration of B increases with time.
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
8
CONCENTRATION OF REACTANT
AGAINST TIME
A(g)  B(g)
Concentration

[A]

Time

9
CONCENTRATION OF PRODUCT
AGAINST TIME
A(g)  B(g)

[B]
Concentration

Time

10
 CONCENTRATION OF REACTANT
AND PRODUCT AGAINST TIME
A(g)  B(g)

[B]
Concentration

[A]

Time

11
 DIFFERENTIAL RATE EQUATION

 shows the relationship between the rate of

disappearance of reactants and formation of products.

Two moles of A disappear for

2A B each mole of B that formed

Rate of disappearance of A : Rate of formation of B :

1 d[A] d[B]
rate = – rate = +
2 dt dt

12
 aA + bB cC + dD

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

rate = – = – =+ =+
a dt b dt c dt d dt

EXAMPLE:

H2(g) + I2(g)  2HI(g)

d[H2] d[I2] 1 d[HI]

rate = – =– =+
dt dt 2 dt 13
 CHAPTER 1.1

EXAMPLE: 1

Write the rate expression (differential rate

equation) for the following reaction:

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)

14
 EXAMPLE: 1

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)

d[CH4] 1 d[O2] d[CO2] 1 d[H2O]

rate = – =– =+ =+
dt 2 dt dt 2 dt

15
 CHAPTER 1.1

EXAMPLE: 2

Hydrogen sulfide burns in oxygen to form sulfur

dioxide and water.

2H2S(g) + 3O2(g)  2SO2(g) + 2H2O(g)

If sulfur dioxide (SO2) is being formed at a rate

of 0.30 mol L–1 s–1, what are the rates of
disappearance of hydrogen sulfide (H2S)
and oxygen (O2)?
16
 EXAMPLE: 2

2H2S(g) + 3O2(g)  2SO2(g) + 2H2O(g)

1 d[H2S] 1 d[O2] 1 d[SO2] 1 d[H2O]

rate = – =– =+ = +
2 dt 3 dt 2 dt 2 dt
d[SO2]
Given, = 0.30 mol L-1 s-1
dt

1 d[H2S] = 1 d[SO2]
– +
2 dt 2 dt

17
 –
d[H2S] = + 1 0.30 mol L–1s–1 X (2)
dt 2

= 0.30 mol L–1s–1

So, rate of disappearance of H2S = 0.30 mol L–1s–1

Or 0.30 Ms-1

18
 EXAMPLE: 2

2H2S(g) + 3O2(g)  2SO2(g) + 2H2O(g)

1 d[H2S] 1 d[O2] 1 d[SO2] 1 d[H2O]

rate = – =– = + =+
2 dt 3 dt 2 dt 2 dt

1 d[O2] 1 d[SO2]
– =+
3 dt 2 dt
d[O2] 3 (0.30 mol L–1s)
– = +
dt 2
= 0.45 mol L–1s–1
So, rate of disappearance of O2 = 0.45 mol L–1s–1 or Ms-1 19
 RATE LAW
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
The rate equation or the rate law :
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 20
 RATE
RATE
CONSTANT
CONSTANT
(k) (k)

aA + bB cC + dD
Rate = k [A]x [B]y

 Proportionality constant for a given

reaction and temperature

 It does not change as reaction proceeds

21
 REACTION ORDERS

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)
 It shows 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. 22
 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

23
 EXAMPLE:
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

24
 OVERALL REACTION ORDER
FROM THE UNIT OF k
Rate = k[A]x

Overall Reaction Units of k

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
 You can always determine
the unit of k mathematically

EXAMPLE:

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

Rate = k[A]3
M = k (M)3
s
k = M–2s–1

= L2 mol–2s–1
 CHAPTER 1.1

EXAMPLE: 3

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
5
(d) order
2
 EXAMPLE: 3
(a) First order A  products
Rate = k[A]
M = k (M)
s
k = s–1

(b) Second order

Rate = k[A]2
M = k (M)2
s
k = M–1 s–1 or L mol–1 s–1
 EXAMPLE: 3
(c) Third order
Rate = k[A]3
M = k (M)3
s
k = M–2 s–1 or L2 mol–2 s–1

5
(d) order
2
5
Rate = k[A] 2
5
M = k (M) 2
s
– 3 3
–
3
2 2 2
k = M s–1 or L mol s–1
 CHAPTER 1.1

EXAMPLE: 4

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]

3/2
(b) CH3CHO(g)  CH4(g) + CO(g); rate = k[CH3CHO]

(c) H2O2(aq) + 3I–(aq) + H+(aq)  I3–(aq) + 2H2O(l);

rate = k[H2O2][I–]
30
 EXAMPLE: 4

(a) 2NO(g) + O2(g)  2NO2(g)

rate = k[NO]2[O2]
 Second order in NO
First order in O2
Third order overall
(b) CH3CHO(g)  CH4(g) + CO(g)
rate = k[CH3CHO] 3/2
 3/2 order in CH3CHO
3/2 order overall 31
 EXAMPLE: 4

(c) H2O2(aq) + 3I–(aq) + H+(aq)  I3–(aq) + 2H2O(l)

rate = k[H2O2][I–]

 First order in H2O2

First order in I–
Zero order in H+
Second order overall

32
 HALF–LIFE (t½ )

 Time required for the concentration

of a reactant to decrease to half of its
initial concentration

33
 ZERO ORDER

 Rate is not dependent on the concentration

of the reactant

Rate = k [A]o Thus, Rate = k

• Zero order in A
• Zero order overall

• Quite common in metal–catalyzed

and biochemical processes 34
 The relationship between the concentration
of the reactants and time
→ INTEGRATED RATE LAW

For zero order reaction :

If the reaction : A  products

Rate = k -d[A]
Rate =
dt
Combining both equation:
-d[A]
=k
dt

35
The integrated rate equation for zero order reaction is:

[A]o – [A]t = kt

OR
[A]t = [A]o – kt

Where:
[A]o = the initial concentration
[A]t = concentration at particular time
t = time of reaction
k = rate constant
 Graph Analysis
(a) From rate law of zero order : Rate = k
Rate

[A]
(b) From the integrated rate law:
(i) [A]t = [A]o – kt (ii) [A]o – [A]t = kt
[A] [A]o – [A]
[A]o

t t
From integrated rate law :

[A]t – [A]o = – kt

t½ = t when [A]t = [A]o/2

[A]o – [A]
o = – kt½
2
[A]o Half-life for zero
– = – kt½ order reaction
2
[A]o
t½ =
2k
 t½ directly proportional to [A]o 38
Determining zero-order reaction from the
graph concentration against time

[ A]
[ A]

1
[ A]
2
1
[ A]
4
t½ (I) t½ (II) time,t
 FIRST ORDER
 Rate is directly proportional to the concentration
of a reactant.
Rate = k[A]
 If [A] double  rate double
[ A ] = [ 2A ]

Rate = k[2A]
Rate = 2k[A]
40
 Rate = k[A]

• First order in A
• First order overall

• EXAMPLE: radioactive reaction

(radioactive decay rates)

41
If the reaction : A  products
is a first-order reaction, therefore;

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

dt
Combining both equation:

-d[A] = k[A]
dt
The integrated rate law for first-order reaction is:

ln[A]o – ln[A]t = kt

OR

[A]
ln  kt
[A]t

OR

ln[A]t = ln[A]o - kt
 Graph Analysis [A]
(a)
[A]o

t
(b) From rate law of first order : Rate = k[A]

Rate

[A]
(c) From the integrated rate law:

i) [ A]
[A] ln
ln  kt [ A]
[A]t

t
(ii) ln[A]t = ln[A]o - kt ln[A]
ln[A]o

t
First order reaction half-life :

[A]o
ln = kt
[A]t

t½ = t when [A]t = [A]o/2

[A]o For first order,

ln t1/2 does not
[A]o/2 depend on [A]o
t½ =
k

t½ = ln 2
k
Determining first order reaction from the
graph concentration against time
[ A]

[ A]

1
[ A]
2
1
[ A]
4
t½ (I) t½ (II) time,t

First order-reaction :
First half life = Second half life
Thus, t½ (I) = t½ (II)
 SECOND ORDER

 Rate is directly proportional to the square

of the concentration of the reactant.

Rate = k[A]2

 If [A] double  rate quadruples

[ A ] = [ 2A ]

Rate = k[2A]2
Rate = 4k[A]2 48
 Rate = k[A]2

• Second order in A

• Second order overall

49
If the reaction : A  products
is a second-order reaction, therefore;

The integrated rate law for second-order reaction is:

1 1
 kt 
[ A]t [A]
or

1 1
-  kt
[ A]t [A]
Second order reaction half-life :

1 1
– = kt
[A]t [A]o

t½ = t when [A]t = [A]o/2

1
t½ =
k[A]o

 t½ inversely proportional to [A]o

 As reaction proceeds, t½ increases

Determining second-order reaction from the
graph concentration against time
[ A]

[ A]

1
[ A]
2
1
[ A]
4
t½ (I) t½ (II) time,t
Second-order reaction :
t½ (II) = 2 t½ (I)
 Graph Analysis
Rate
Rate

[A]2
[A]

From rate law of second order : Rate = k[A]2

From the integrated rate law
1 1
 kt 
[ A]t [A]
1
[ A]

1
[ A]

time,t
From the integrated rate law:

1 1
  kt
[ A]t [A]
1 1

[ A] [A]

time,t
 EXAMPLE: 5

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 ?

56
 EXAMPLE: 5

The reaction is zero order reaction

[A]t – [A]o = – kt

t = 100 minute = 6000 s

[A]t = – kt + [A]o

[A]t = –(1.65 x 10-5 M s-1)(6000 s) + 1.00 M

[A]t = 0.901 M
57
 EXAMPLE: 6

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 .

58
 EXAMPLE: 6

The reaction is zero order reaction

[A]o
t½ =
2k

1.2 M
t½ =
2(0.00624 M s-1)

t½ = 96.15 s
59
 CHAPTER 1.1

EXAMPLE: 7

N2O5 decomposes into N2O4 and O2.

2N2O5(g)  2N2O4(g) + O2(g)
At 45oC, 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?
 EXAMPLE: 7

2N2O5(g)  2N2O4(g) + O2(g)

The reaction is first–order overall.

[N2O5]o
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 = ?
 EXAMPLE: 7
[N2O5]o
ln = kt
[N2O5]t

[0.500 M]
ln = 6.22 x 10–4 s–1 x 3600 s
[N2O5]t

(0.500 M)
[N2O5]t = 9.3858

[N2O5]t = 0.0533 M
 CHAPTER 1.1

EXAMPLE: 8

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 ?
 EXAMPLE: 8

2A  B  first order reaction

[A]o = 0.88 M
[A]o
ln = kt
[A] = 0.14 M [A]t
k = 2.8 x 10–2 s-1

[A]o 0.88 M
ln ln
[A]t 0.14 M
t = =
k 2.8 x 10–2 s-1

= 66 s
 CHAPTER 1.1

EXAMPLE: 9

What is the half–life (in min) of N2O5 if it decomposes

with a rate constant of
5.7 x 10–4 s–1?
 EXAMPLE 9:

The unit of k = s–1

 First order reaction

ln2 0.693
t½ = =
k 5.7 x 10–4 s–1

= 1216 s

= 20.27 min
 CHAPTER 1.1

EXAMPLE: 10

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.
 EXAMPLE: 10
I(g) + I(g)  I2(g)
The reaction is second–order overall.

1 1
= + 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 = ?
 EXAMPLE: 10
1 1
= + kt
[I]t [I]o

1 1 + (7.0 x 109 M–1s–1) x 120s

=
[I]t 0.086 M

= 8.4 x 1011 M–1

[ I ]t = 1.190 x 10–12 M
 CHAPTER 1.1

EXAMPLE: 11

The rate constant of the reaction 2A  B

is 51 M-1min-1 at 24oC.
(a) Starting with [A] = 0.0092 M, how long will it
take for [A] = 3.7 x 10–3 M?
(b) Calculate the half–life of the reaction.
 EXAMPLE: 11

2A  B
(a)
k = 51 M–1 min–1

The reaction is second–order overall.

1 1 [A]o = 0.0092 M
= + kt
[A]t [A]o [A] = 3.7 x 10–3 M t =?

1 1
= + ( 51 M–1min–1 ) x t
3.7 x 10–3 M 0.0092 M

t = 3.168 min
 EXAMPLE: 11

(b) 2A  B
k = 51 M–1 min–1
The reaction is second–order overall.

1
t½ = [A]o = 0.0092 M
k[A]o

1
=
(51 M–1 min–1 )(0.0092 M)

= 2.131 min
METHODS TO DETERMINE ORDER OF
REACTION :

1 • INITIAL RATE METHOD

2 • LINEAR GRAPH
METHOD

3 • HALF-LIFE METHOD

73
 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
 CHAPTER 1.1

EXAMPLE: 12

Determine the rate law and calculate the rate

constant for the following reaction from the following
data:
F2 (g) + 2ClO2 (g) 2FClO2 (g)

Initial Rate
Experiment [F2] [ClO2]
(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
 EXAMPLE: 12
Initial Rate
Experiment [F2] [ClO2]
(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
1.2 x 10-3 (0.1)x
(2.0)1 = (2.0)x x = 1  first order in F2
 EXAMPLE: 12
Initial Rate
Experiment [F2] [ClO2]
(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
= =-3
Rate 1 k[F2]x[ClO2]y 1.2 x 10 k[0.1]x[0.01]y
4.8 x 10-3 (0.04)y
-3
=
1.2 x 10 (0.01)y
(4.0)1 = (4.0)y y = 1  first order in ClO2
 EXAMPLE: 12

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
 EXAMPLE: 13
Consider the reaction between nitrogen dioxide, NO 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
79
 EXAMPLE: 13
NO2(g) + CO(g) → NO(g) + CO2(g)
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

Rate = k[NO2]x[CO]y
 Find order in NO2 with [CO] 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 80
 3.9 = (2.0)x
x = 2  second order in NO2

 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 ]x[CO]y 0.0082 k[0.20]x[0.10]y

0.0083 = (0.20)x
0.0082 (0.10)x

1.01 = (2.0)y
y = 0.01 NO2
y = 0  zero order in NO2 81
 EXAMPLE: 13

Rate = k[NO2]x[CO]y

x = 1, y = 0 rate = k[NO2]2[CO]0

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

0.0021 M s–1 = k(0.10 M)2(0.10 M)0

k = 0.21 M–1s–1
 2 : LINEAR GRAPH METHOD
The reaction order also can be determined by
the integrated rate law !

How ?

By plotting the graph !

 look for the linear graph

Which graph ?
Which one ???

I don’t know. Just

try-and-error!
 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
Plot ln[reactant] vs. time:
linear graph  first order

Plot 1/[reactant] vs. time:

linear graph  second order

Plot [reactant] vs. time:

linear graph  zero order
EXAMPLE:

 The reaction is first order in N2O5

 CHAPTER 1.1

EXAMPLE: 14
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
 EXAMPLE: 14

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

 EXAMPLE: 14

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

Plot [C2H5I] vs. time:

If a linear graph obtained  zero order
 EXAMPLE: 14
ln [C2H5I] The reaction is first–order.
ln [C2H5I]o k = – slope
= – (– 1.3 x 10–2 min–1)
= 1.3 x 10–2 min–1

slope = – k

Time (min)
 3: HALF-LIFE METHOD
EXAMPLE 15

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 91
 EXAMPLE: 15

Plot [A] 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
GRAPH [ C2H5 ] AGAINST TIME

0.90

0.80 1st t1/2 = 2nd t1/2 = 70 min

0.70

0.60
[C2H5], M

0.50

0.40

0.30

0.20

0.10

0.00
0 25 50 75 100 125 140150 175 200 225 250
70 Time, (min)
1st 2nd t1/2
93
t1/2
 EXAMPLE: 15

First half life = Second half life

t½ (I) = t½ (II)

Thus, the reaction is first order-reaction

Half-life = 70 minute (from the graph)

ln2
t½ =
k

ln2 0.693
k= = = 9.9 x 10-3 min-1
t½ 70 min
94
 Zero order 1st order 2nd order
A  product A  product A  product
rate = k [A] rate = k [A]2
rate = k
Unit k = Ms-1 Unit k = s-1 Unit k = M-1 s-1

rate rate
rate
[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
1/[A]
ln[A]

ln[A]0
1/[A]0
t
t
END OF
1.1