OBJECTIVES

Determine order of reaction involving a

single reactant using
• Initial rate method
• The units of rate constants,k
• Half-life based on the graph of concentration
against time
• Linear graph method based on the
integrated rate equation and rate law

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DETERMINATION THE ORDER OF A
REACTION

THE INITIAL RATE METHOD

2
 DETERMINATION THE ORDER OF A
REACTION
1) THE INITIAL RATE METHOD
 Compare the initial rate at difference
concentration

Rate exp 1 =k[A1][B1]

Rate exp 2 k [A2][ B2]

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 Example
[ ] mol dm-3 Initial Rate
Exp [A] [B] (Ms-1)

1 0.50 1.0 2.0

2 0.50 2.0 8.0
3 0.50 3.0 18.0
4 1.00 3.0 18.0
a) Determine the order of the reaction
b) Write the rate law
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 Solution
• To determine the order with respect to A
From exp. 3 & 4 ( keep [ B ] constant )

Rate exp 3 = k[A3] x[B3]y

Rate exp 4 k [A4]x[B4]y

18.0 Ms-1 = k (0.5)x(3.0)y

18.0 Ms-1 k (1.0)x(3.0)y
x =0
 ZERO - ORDER with respect to A
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• To determine the order with respect to B
From exp 1 & 2 ( keep [ A ] constant )
Rate exp 1 = k[A1] x[B1]y
Rate exp 2 k [A2]x[B2]y

2.0 Ms-1 = k (0.5)x(1.0)y

8.0 Ms-1 k (0.5)x(2.0)y
y =2
 SECOND-ORDER with respect to B

b ) Rate law, rate = k [ B ]2

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DETERMINATION THE ORDER OF A
REACTION

UNITS OF RATE CONSTANTS,k

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2) UNITS OF RATE CONSTANTS,k

ORDER Unit of
k
ZERO Ms-1

FIRST s-1

SECOND M-1s-1

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 EXAMPLE
The conversion of cyclopropane to propene in
the gas phase with a rate constant of 6.7 x 10-4 s-1 at
500 0C.
a) If the initial concentration of cyclopropane
was 0.25 M what is its concentration after 8.8min

b) How long will it take for the concentration of

cyclopropane to decrease from 0.25M to 0.15M

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 Solution

a) first order reaction (from the unit of k = s-1)

ln [A]0 = 6.7 x 10-4 X (8.8 X 60)
[A]
[A] = 0.175 M
b) ln 0.25 = 6.7 x 10-4s-1 x t
0.15
t = 762.42 s

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 EXAMPLE

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

i) If the initial concentration of iodine was 0.086 M,

calculate it’s concentration after 2 min.
ii) Calculate the half life of the reaction if the
initial concentration of iodine is 0.06 M and
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0.42 M respectively.
 Solution
1 1
i) = Kt +
[A] [A]0
1
= (7.0 x 109 x 2 x 60 ) + 1
[A]
[0.086]

[A] = 1.190 x 10-12 M

ii) [I2]0 = 0.06 M
1 1
t1/2= =
k[A]0 (7.0 x 10 x 0.06)
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= 2.38 x 10-9 s
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DETERMINATION THE ORDER OF
A REACTION

GRAPHICAL METHOD
• HALF-LIFE based on the
GRAPH of [ ] vs time

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 3) Graphical method
a) HALF-LIFE METHOD
Plot the GRAPH [ ] VS t
 ZERO-ORDER REACTION

[ A]
k
2t 1
2

VIDEO 11
14
 0.693 1
k VIDEO 12
k VIDEO 13

t1 [ A]0 t 1
2 2
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 EXAMPLE

The following results were obtained from an

experimental investigation on dissociation of
dinitrogen pentoxide at 45oC
N2O5(g)  2 NO2(g) + ½ O2(g)
time, t/min 0 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
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[N2O5] x 10-4 M Solution
180 i. First order because the half life
160 is not depending on the initial
concentration
140
ii. 0.693
120 k = ln 2 / t1/2 = 0.693 / 20
100 t1
2 = 0.035 min -1
80
60
40
20

10 20 30 40 50 60 70 80
Time ( min)
t1/2 t1/2 17
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

ii) k = ln 2
= 0.03 min-1
20 min

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DETERMINATION THE ORDER OF A
REACTION

4) GRAPHICAL METHOD
LINEAR GRAPH METHOD based on
• INTEGRATED RATE EQUATION
AND
• RATE LAW

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 4 ) LINEAR GRAPH METHOD
ZERO-ORDER REACTION
Based on the RATE LAW Based on the
INTEGRATED RATE EQ

Rate [A]0 – [A]

Rate = k
k = M s-1

[A] [A]0 - [A] = k t t

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 FIRST-ORDER REACTION
Based on the RATE LAW Based on the
INTEGRATED RATE EQ

Rate ln [A]0/[A]

Rate = k [A]
k = s-1

[A] ln([A]o/[A]) = kt
t21
 SECOND -ORDER REACTION
Based on the RATE LAW

A → product
rate

Rate = k [A]2
k= M-1s-1
[A]2

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Based on the
SECOND ORDER INTEGRATED RATE EQ

1/[A]

t
1 =k t + 1
[A] [A]0
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Based on the
SECOND ORDER INTEGRATED RATE EQ

1 - 1 = kt
1/[A] – 1/[A]0 [A] [A]0

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