Ch.

III: Rate Law Third method

Methods for the determination of the reaction order
3- Integral method
• Each rate law led by integration to a different relation
C = f (C0, t)
3.1- Graphic verification
-Transforming the integrated expression into
a form of the equation of a line
-Plot the points in a graph and check that they
are well aligned

3.2- Numerical verification :

- calculating k for each point
- making sure that these values are visibly constant
 Ch. III: Rate Law Third method
Methods for the determination of the reaction order

3- Integral method
[A] = [A]0e-kt
3-1- Graphical method
CH3NC → CH3CN

This is indicative of a first order reaction

Isomerisation is always first order
 Ch. III: Rate Law Third method
Methods for the determination of the reaction order
3- Integral method
3-1- Graphical method CH3NC → CH3CN

We try to see whether the value of t1/2 remains constant

t1/2 = (ln 2) / k
 Ch. III: Rate Law Third method
Methods for the determination of the reaction order
3- Integral method
3-1- Graphical verification 2 NO2 → 2 NO + O2
 Ch. III: Rate Law Third method
Methods for the determination of the reaction order
3- Integral method
3-2- Numerical verification

We calculate the reaction constant by supposing that

the reaction is successively of order 1, 2 and 3

C2H5NH2 → C2H4 + NH3

Order 1 Order 2 Order 3

𝟏 [𝑨] 𝟏 𝟏 𝟏 𝟏 𝟏 𝟏
𝐤= 𝐋𝐧 𝟎 k= ( - ) k= ( - )
𝒕 [𝑨] 𝒕 [𝑨] [𝑨]𝟎 𝟐𝒕 𝑨 𝟐 [𝑨]𝟐𝟎
3- Integral method
3-2- Numerical method C2H5NH2 → C2H4 + NH3
t (s) 0 100 200 300 400 500 600

[A] mol.l-1 5 3.55 2.75 2.25 1.85 1.6 1.48

Order 0 [𝑨]𝟎 −[𝑨] 14.5x10-3 11.25x10-3 9.17x10-3 7.88x10-3 6.8x10-3 0.2x10-3

𝐤=
𝒕

Order 1 𝟏 [𝑨]𝟎 3.43x10-3 2.98x10-3 2.66x10-3 2.48x10-3 2.27x10-3 2x10-3

𝐤 = 𝐋𝐧
𝒕 [𝑨]

Order 2 𝟏 𝟏 𝟏 8.17x10-4 8.18x10-4 8.15x10-4 8.53x10-4 8.5x10-4 7.93x10-4

k= ( - )
𝒕 [𝑨] [𝑨]𝟎

Order 3 𝟏 𝟏 𝟏 1.97x10-4 2.3x10-4 2.63x10-4 3.15x10-4 3.5x10-4 3.47x10-4

k= ( 𝟐 - 𝟐)
𝟐𝒕 𝑨 [𝑨]𝟎

Order is 2 since the rate law is verified by calculating k at different time and
it reveals almost constant
k (average)= 8.24 x10-4 M-1.s-1
 Ex 3 page 104 or 106; During the kinetic studies of the reaction of pyridine with
ethyl iodide, the concentration of iodide ions has been measured at different
times. Initial concentrations for both reagents are 0.1 mol.dm-3.
Determine the reaction order relative to the pyridine and the rate constant.
1 1
C5H5N + C2H5I → C7H10N+ + I- (𝑎 − 𝑥) − 𝑎 = 𝑘𝑡
t= 0 a a 0 0
t a-x a-x x x a = 0.1 M
ꚙ 0 0 a a

x → [I-] 10-3mol.dm-3 15 26 35 44 52 59 64
ts 235 465 720 1040 1440 1920 2370
a-x 0.085 0.074 0.065 0.054 0.048 0.041 0.036
𝟏 𝟏
− = 1.76 3.51 5.38 8.51 10.83 14.39 17.77
(𝒂 − 𝒙) 𝒂
 Graphical verification Ex 3 page 106 or 104
20

18 y = 0,0075x + 0,1362
R² = 0,9979
16

14

12

10 Rate constant k =0.0075 M-1.s-1

8

0
0 500 1000 1500 2000 2500

Or Numerical verification
[I-] 10-3mol.dm-3 15 26 35 44 52 59 64
ts 235 465 720 1040 1440 1920 2370
𝟏 𝟏
− = 1.76 3.51 5.38 8.51 10.83 14.39 17.77
(𝒂 − 𝒙) 𝒂
𝟏 𝟏 𝟏 7.489 7.54 7.47 8.18x 7.52 7.49 7.498
k=( − )
(𝐚−𝐱) 𝐚 𝐭 x 10-3 x 10-3 x 10-3 10-3 x 10-3 x 10-3 x 10-3
The law is verified since k is constant => k (average)= 7.59 x 10-3 M-1.s-1