Differential and integrated rate laws

Consider A B: a) 0th Order

d[A]

=k
dt
Differential rate law

[ A](t)

[A]0

d[A] = k dt

d[A] = k dt

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

[A](t) = [A]0 k t
Integrated rate law

b) 1st Order

d[A]

= k[A]
dt

[ A](t)

d[A]
= k dt

[A]
[ A ]0
0

[A](t) = [A]0 e k t
Integrated rate law

Differential rate law

[A](t)
= k t
ln[A](t) - ln[A]0 = ln
[A]0

Nils Walter: Chem 260

Differential and integrated rate laws of a

second order reaction
c) 2nd Order

d[A]

= k[A]2
dt

[ A](t)

d[A]
= k dt
2

[A]
[ A ]0
0

Differential rate law

[ A](t)

1
1
1
= k t

[A] [ A]0
[A](t) [A]0

1
1
= kt +
[A](t)
[A]0

[A]0
[A](t) =
1 + k t[A]0

Integrated rate law

Nils Walter: Chem 260

The half-life of a reaction

Half-Life
Half-Lifeof
ofaaReaction:
Reaction:
The
Thetime
timerequired
requiredfor
for[A]
[A]to
todrop
dropby
byaafactor
factorof
oftwo
two
0th Order: [A](t) = -kt + [A]0

1st Order: [A](t) = [A]0 e-kt

[A]0/2 = -kt + [A]0

[A]0/2 = [A]0 e-kt

kt = [A]0 - [A]0/2

2nd Order:
2
[A]0

t1 =
2

[A]0
2k

1
[A](t)

= kt +

e-kt = 1/2

= kt +

1
[A]0

ln2
k

Independent
of [A]0!

1
[A]0
kt =

t1 =

2
[A]0

1
[A]0

t1

1
=
k[A]0

Nils Walter: Chem 260

Summary of rate laws

Differential
Rate Law
0th

1st

2nd

Order:

d[A]

=k
dt

Order:

d[A]

= k[A]
dt

Order:

d[A]
2

= k[A]
dt

Integral
Rate Law

Half-Life

[A](t) = [A]0 k t
[A](t) = [A]0 e

k t

1
1
= kt +
[A](t)
[A]0

t1

[A]0
=
2k

t1 =
2

t1

ln2
k

1
=
k[A]0

Nils Walter: Chem 260

Tricks to determine rate laws

Consider A B:
0th

2nd

[A](t) = k t + [A]0

Order:

1st Order:

Order:

Consider A + B C :

ln[A](t) = k t + ln[A]0
1
1
= kt +
[A](t)
[A]0

Linear regression

= mx

+b

2nd Order:

d[A]

= k[A][B]
dt

BUT by
a) choosing [A]0 = [B]0
[A] = [B] !

d[A]

= k[A]2
dt

b) choosing [A]0 << [B]0 [B] constant !

d[A]

= k'[A]; k' = k[B]0

dt

Nils Walter: Chem 260

Sample
SampleProblem:
Problem:
Consider: CH3CH2NO2 + OH- CH3CHNO2- + H2O
Initially [CH3CH2NO2] = [OH-] = 5.00
10-3 M. The concentration of
hydroxide was then measured by monitoring the pH with the following result.
What is the order of the reaction? What is k?
t (min)
[OH-] (M)
[OH-]-1

0
5.00
10-3
200

10

15

2.6
10-3
385

1.7
10-3
588

1.3
10-3
769

The most reasonable initial guess for this reaction is:

-d[OH-]
= k [OH-][CH3CH2NO2] = k [OH-]2
dt
1
Good line (r = 0.9998) correct rate law
slope = k = 0.637 M-1 s-1

1
[OH-]

= kt +

1
[OH-]0

800
670
540

[OH-]410
280
150

250 500 750 1000

Nils Walter: 0Chem
260
Time (s)