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Integrated Rate Law

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 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
- d[A] = k
dt
Using calculus,
- d[A] = kdt
- ∫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


Graphs for zero order reaction

[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)

Half life (t½) is the time required for the


concentration of a reactant to decrease to half of its
initial value.

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
First Order Reactions

A first order reaction is a reaction whereby its


rate depends on the concentration of reactant
raised to the first power.
From the rate law,
rate = k[A]
To obtain the units of k
k = rate
[A]

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

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

ln[A]o
ln[A]o
[A]

t t
Example

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
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10 s
-2 -1
Example
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) [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,

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 500°C.

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)
Half-life of a first-order reaction
The half-life, t½, is the time required for the concentration of a
reactant to decrease to half of its initial concentration.
t=t½ when [A] = [A]0
2
[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1 ?
t½ = ln2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s
-4 -1

How do you know decomposition is first order?


units of k (s-1 )
First-order reaction
A product

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

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 3

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. Ans (91.20 )
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 = - = k[A]2
dt
To obtain the units of k
rate
k =
[A]2
Unit k = M/s
M2
= M-1 s-1

Using calculus, the following expression can be obtained


1 - 1
= + kt
[A] [A]0
Characteristic graphs for second order reaction

Rate = k [A]2
rate

[A]

rate

[A]2
Graphs for second order reaction

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

1/[A] M-1 1/[A] – 1/[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

R will increase by 4 times if [A] doubles


Half life of a second order reaction
1 1 + kt
=
[A] [A]0

[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

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 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

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

Plot graph of [N2O5] vs time, determine


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

1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln2


k
1 1 1
2 rate = k [A] 2 = + kt t½ =
[A] [A]0 k[A]0
Zero order 1st order 2nd order
A → product A → product A → product
r = k [A]0 r = k [A]1 r = k [A]2
Unit k = M s-1 Unit k = s-1 Unit k = M-1 s-1
r r r r

[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

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


ln2/k
t t t