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Objectives:
1.Write the rate law for zero order, 1st order and
2nd order reaction
2. Define half-life.
3. Draw the respective graphs for the different
order reactions
4. Solve quantitative problems.
Integrated rate equations
Zero Order Reaction
A→ product
rate
[A]0 -[A] = kt
[A]o – [A] = kt
[A]o – [A]
y = mx + c
[A] rate
[A] = -k t + [A]o
[A]o
y=m x+c
t [A]
Half-life (t½)
unit k = M s-1
M
= s-1
Rate = k[A]
y = mx + c
Rate
Ms-1
[A] ,M
For first order reaction,
Rate = k[A]
- d[A] substituting
= k[A]
dt
t = 0, [A]=[A]0
- d[A] = k dt
[A] - ln [A]0 = k(0) + c
- d[A] = k dt c = − ln[A]0
∫ ∫
[A] -ln [A] = kt – ln[A]0
- ln [A] = kt + c
[A]0
ln = kt
[A]
Characteristic graphs of 1st order reaction
ln[A]o – ln[A] =kt
[A]0
ln ------ = kt
t [A]
ln[A]
ln[A]o
ln[A]o
[A]
t t
Example
Solution :
a) [H2O2]0
ln = kt
[H2O2]
ln 0.882 = 3.66 x 10-3 s-1 x t
0.600
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]
0.882
ln = 3.66 x 10-3 s-1 x 225 s
[H2O2]
[H2O2] = 0.387 M
Exercise,
CH2
CH2 CH2 CH3-CH=CH2
No. of
half-lives [A]o = 8 M
1 4
2 2
3 1
4 1/2
t½ = ln2
k
Example
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 ln 2
t1/2 =
k
0.693
=
5.36 x 10-4
= 1.29 x 103 s
= 21.5 min
Problem 2
Example
A→ product
Where
d[A]
Rate = - = k[A]2
dt
To obtain the units of k
rate
k =
[A]2
Unit k = M/s
M2
= M-1 s-1
Rate = k [A]2
rate
[A]
rate
[A]2
Graphs for second order reaction
[A] 1 1
= + kt
[A] [A]o
1/[A]o
t t
2 –order reaction, r = k[A]
nd 2
If [A] doubles,
r2 = k (2[A])2
= k ( 4 [A]2 )
= 4 k [A]2
= 4r
[A]= [A]o
Substituting t = t1/2 2
1 1 + kt1/2
=
[A]0 [A]0
2
1
t1/2 =
k[A]0
Detemination of half-life using graph for
[A]0 second order reaction
1
t1/2 =
k[A]0
[A]0/2
[A]0/4
[A]0/8
x 2x 4x t
Example
Iodine atoms combine to form molecular iodine in
the gaseous phase
0.42 M respectively.
Solution :
1 1 + kt
i) =
[A] [A]0
1 1 + (7.0 x 109
x 2 x 60 )
=
[A] [0.086]
= 8.4 x 1011
[A] = 1.190 x 10-12 M
ii) [I2] = 0.06 M
1 1
t1/2 = =
k[A]0 7.0 x 10 x 0.060
9
= 2.4 x 10-10 s
[I2] = 0.42 M
1
t1/2 =
k[A]0
1
=
7.0 x 109 x 0.042
= 3.4 x 10-10 s
Using graph
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
160
140
120
[N2O5] x 100
10-4 /M 80
60
40
20
10 20 30 40 50 60 70 80
Time ( min)
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 = ln2
= 0.03 min-1
20 min
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k
[A] [A]
[A] [A]2
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] t1/2 = [A]0/2k [A] ln[A] [A] 1/[A]
[A]0 ln[A]0
1/[A]0
t t t t t
[A]0 - [A]
ln([A]0 / [A]) 1/[A] – 1/[A]0