Chemical

Kinetics
Chapter I
Peter Atkins, Physical Chemistry, 7
th
edition
Jeffrey I. Steinfeld et al, Chemical Kinetics and Dynamics, 2
nd
edition
Basic concepts of kinetics
Thermodynamics
First law
Second law
Third law
Kinetics
Deal with changes of the
system properties in time.
(Physical-Chemical)
Feasibility of any process
or reacction to take place
(AS
Univ
. > 0, AG < 0)
a) Rate of a chemical reaction:
Chemical kinetics: Study chemical systems whose
composition changes with time
!Gas, liquids, solid
Homogeneous: Single-phase

Heterogeneous: Multi-phase
Stoichiometric representation
aA + bB + cC + dD
a and b: # of moles of A and
B, i.e. the reactants

c and d: # of moles of C and
D, i.e. the products
Irreversible
Chemical reaction
Reversible
Chemical reaction
2H
2
+O
2
2H
2
O H
2
+ I
2
2HI
Type of reactions:
Elementary: One step

Complexes: Multi-steps
Rate of reaction: Change in composition of the reaction mixtures
| | | | | | | |
dt
D d
d dt
C d
c dt
B d
b dt
A d
a
R
1 1 1 1
= = = =
Reac. [i] (-) Prod. [j] (+)

I
2
+ hv I
2
*
I
2
* 2I
2I + M I
2
+ M
H
2
+
2
I 2HI
b) Order and Molecularity of a chemical reaction:
One or more reactants
[i]s
One or more intermadiates
[E]s
One or more species that do
not appear in the reaction
[C]
Reaction rate
R = f([A], [B])
R o [A]
m
[B]
n
m and n: Integer, fractional or
negative
R = k [A]
m
[B]
n
Rate equation!
Rate constant
(Proportionality constant)
m: Order of reaction with
respect to A.
n: Order of reaction with
respect to B
p = m + n : Overall order of
reaction
http://www.chem.uci.edu/education/undergrad_pgm/applets/sim/simulation.htm
General expression
[
=
=
k
i
n
i
i
c k R
1
n
i
: Reaction order with respect
to is component.



*Units of K : [i]
-(p-1)
t
-1

=
=
k
i
i
n p
1
Elementary reactions are described by their molecularity
Molecularity: # of reactants involved in the reaction step! (always an integer)
Spontaneous
decomposition

A and B react
with each other

Three reactants
that comes together
A Products Unimolecular


A + B Products Bimolecular


A + B + C Products Termolecular
http://www.chm.davidson.edu/ChemistryApplets/kinetics/ReactionRates.html
Elementary reaction rate laws
Time behavior Integrating the rate law
a) Zero-Order reaction:
kt A A kt A A
t
dt k A d k
dt
A d
A a
A k
dt
A d
a
R
t t
t
t
A
A
t
= =
=
= =
= =
= =
} }
0 0
0
] [
] [
0
0
] [ ] [ ] [ ] [
0
] [
] [
1 ] [ , 1
] [
] [ 1
0 0
t
[A]
t
[A]
0
m = -K
a) A products
Heterogeneous reactions
b) First-Order reaction:
kt
t
t
e A A
kt
A
A

=
=
0
0
] [ ] [
] [
] [
ln
303 . 2
] log[ ] log[
] ln[ ] ln[
] [
] [
] [
] [
] [
] [ 1
0
0
0
] [
] [
1
0
kt
A A
kt A A dt k
A
A d
kdt
A
A d
A k
dt
A d
a
R
t
t
t
A
A
t
=
= =
= = =
} }
a = 1
t
0
=0
t
log[A]
t
log[A]
0
m = -k/2.303
t
[A]
t
[A]
0
t
e-1
[A]
0
k-1
= t (Decay time)
[A]
t
= [A]
0
/e
e=2.7183
b) A products
CH
3
NC CH
3
CN
(CH
3
)
3
CBr +H
2
O (CH
3
)
3
COH +HBr
[90% acetone & 10% water]
T (min) [C] (mol/L)
0 0.1056
9 0.0961
18 0.0856
24 0.0767
40 0.0645
54 0.0536
72 0.0432
105 0.0270
0 20 40 60 80 100 120
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
[
C
]

(
m
o
l
/
L
)
t (min)
Kt A A
t
=
0
] [ ] [
0 20 40 60 80 100 120
0.1
l
o
g
[
C
]

(
m
o
l
/
L
)
t (min)
303 . 2
] log[ ] log[
0
Kt
A A
t
=
c) Second-Order reaction:
c
1
) A + A products
kt
A A
dt k
A
A d
kt
A A
x x
dx
kdt
A
A d
A k
dt
A d
R
t
t
A
A t
t
2
] [
1
] [
1
2
] [
] [
2
] [
1
] [
1
1
2
] [
] [
] [
] [
2
1
0
0
] [
] [
2
0
2
2
2
0
+ =
= =
=
= = =
} }
}
t
[A]
t
-1
[A]
0
-1
m = 2k
2CH
3
C
2
H
6
b



a
b


a
c
2
) A + B products
( ) ( )
( )( )
( )( ) ( )( ) ( )( )
( )
( )
( )
kt
B A
B A
B A
b ax
a b ax
dx
x A B A
dx
x B B A
dx
x B x A
dx
x B x A k
dt
dx
B B A A x
B A k
dt
A d
R
t
t
t t
=
|
|
.
|

\
|

+ =
+

=

=
= =
= =
}
} } }
] [ ] [
] [ ] [
ln
] [ ] [
1
) ln(
1
] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [
] [ ] [
] [ ] [ ] [ ] [
] [ ] [
] [
0
0
0 0
0 0 0 0 0 0 0 0
0 0
0 0
1 1
H
2
+ O OH + H
b



a
b


a
d) Third-Order reaction:
d
1
) A + A + A products
kt
A A
dt k
A
A d
kt
A A
x n x
dx
kdt
A
A d
A k
dt
A d
R
t
t
A
A t
n
b
a
n
t
6
] [
1
] [
1
3
] [
] [
3
] [
1
] [
1
2
1
1
) 1 (
1
3
] [
] [
] [
] [
3
1
2
0
2
0
] [
] [
3 2
0
2
1
3
3
0
+ =
= =
|
|
.
|

\
|

+
=
= = =
} }
}
t
[A]
t
-2
[A]
0
-2
m = 6k
b



a
I + I + M I
2
+ M

d
2
) A + A + B products
( ) ( )
( ) ( )
( )
kt
B A
B A
B A
A A B A
kdt
y B y A
dy
y B y A k
dt
dy
B A
y B B
y A A
B A k
dt
A d
R
t
t
t
t
t
=
|
|
.
|

\
|

+
|
|
.
|

\
|

=

=
=
=
= =
] [ ] [
] [ ] [
ln
] [ 2 ] [
1
] [
1
] [
1
] [ 2 ] [
1
] [ 2 ] [
] [ 2 ] [
] [ , ] [
] [ ] [
2 ] [ ] [
] [ ] [
] [
2
1
0
0
2
0 0
0 0 0
0
2
0
0
2
0
0 0
0
0
2
Partial fractions!
t k
A A
order pseudo B k k
A k
dt
A d
R
t
nd
' 2
] [
1
] [
1
2 ], [ '
] [ '
] [
2
1
0
2
+ =
=
~ =
[B]>>[A]
[B] = const.
O + O
2
+ M O
3
+ M
d
3
) A + B + C products
] ][ ][ [
] [
C B A k
dt
A d
R = =
Reaction rate for n order respect with only one reactant
| |
kt n n
A A
nkt
A A n
dt nk
A
A d
A k
dt
A d
n
R
n n
t
n n
t
A
A
t
n
n
t
) 1 (
] [
1
] [
1
] [
1
] [
1
) 1 (
1
] [
] [
] [
) (
1
) 1 (
0
) 1 ( ) 1 (
0
) 1 (
] [
] [ 0
0
=
|
|
.
|

\
|
=
|
|
.
|

\
|

=
= =

} }
e) Reaction half-lives:
Alternative method to
determine the reaction order
2
] [
] [
0
2
1
2
1
A
A t =
2 ln
1
] [
2 / ] [
ln
2 / ] [ ] [
] [
] [
ln
2 / 1
2 / 1
0
0
0
0
k
t
kt
A
A
A A
kt
A
A
t
t
=
=
=
=
First-order reaction
For a reaction of order n>1 in a
single reactant
Independent of [A]
0
( )
1
0
1
2
1
] )[ 1 (
1 2

=
n
n
A n k
t
This is function of [A]
0
1
st
order reaction half-lives:
0 10 20 30 40 50
0
0.2
0.4
0.6
0.8
1
1
6.738 10
3

A t ( )
50 0 t
T dependence of the rate constant, k
The Arhenius equation:
k(T)
:

[i]
t
pH (only in solution)
T! (Strongly)
(

=
T k
E
T
B
Act
Ae k
) (
1/T
ln[k
(T)
]

lnA

m = -E
Act
/k
B

Chemical coordinates
E

E
Act
(F)
E
Act
(R)
Reac
Prod.
AH
0
Rxn
A :Frequency factor
0
Re
0
Pr
0
0
) ( ) (
ac od Rxn
Act Act Rxn
H H H
F E R E H
A A = A
= A
Ineffective Effective
Determinant Parameters
Catalysis
Complex reactions
a) Reversible reactions:
A
1
A
2
k
f
k
r
| |
| | | |
| |
| | | |
1 2
2
2 1
1
A k A k
dt
A d
A k A k
dt
A d
f r
r f
=
=
If @ t=0
[A
1
] = [A
1
]
0
[A
2
] = [A
2
]
0
[A
1
] + [A
2
] = [A
1
]
0
+ [A
2
]
0
[A
2
] = [A
1
]
0
+ [A
2
]
0
- [A
1
]
| |
| | | | | | ( ) | |
| |
| |( ) | | | | ( )
0
2
0
1 1
1
1
0
2
0
1 1
1
A A k k k A
dt
A d
A k A A k A k
dt
A d
r r f
r r f
+ + =
+ + =
(Mass conservation law)
Cl Cl
Cl
Cl
| |
( )
| | | | ( )
( )
| |
(
(

+
+
+
+ =
1
0
2
0
1
1
A
k k
A A k
k k
dt
A d
r f
r
r f
Introducing the variable m
| | | | ( )
( )
| |
( ) | | | |
| |
| | | |
| |
| |
( )
| | | |
| | | |
( )t k k
A k A k
A k A k
dt k k
A m
A d
A m k k
dt
A d
k k
A A k
m
r f
r f
r f
t
t
r f
A
A
r f
r f
r
+ =
(
(

+ =

+ + =
+
+
=
} }
0
2
0
1
2 1
1
1
1
1
0
2
0
1
ln
0
1
0 1
| | | |
| |
( )t k k
A k
A k A k
r f
f
r f
+ =
(
(

0
1
2 1
ln
If @ t=0
[A
2
]
0
=0
| |
| |
( )
( )
| |
| | | | | |
| |
| |
( )
( )
| |
t k k
r f
f
t k k
f r
r f
r f
r f
e
k k
A k
A
A A A
e k k
k k
A
A
+
+

+
=
=
+
+
=
1
0
1
2
1
0
1 2
0
1
1
When the equilibrium is reached
| | | |
| | | |
| | | |
| |
| |
eq
eq
eq
r
f
eq
r
eq
f
eq
r
eq
f
K
A
A
k
k
A k A k
A k A k
dt
A d
dt
A d
= =
=
= +
= =
1
2
2 1
2 1
2 1
0
0
b) Consecutive reactions:
A
1
A
2
A
3
k
1

k
2
| |
| |
| |
| | | |
| |
| |
2 2
3
2 2 1 1
2
1 1
1
A k
dt
A d
A k A k
dt
A d
A k
dt
A d
=
+ =
=
b
1
) First:
| | | |
t k
e A A
1
0
1 1

=
b
2
) Second:
For [A
2
] Linear differential equation of first order
| |
| | | |
| |
| | | | | | | |
| |
( )
| |
| |
( )
t k t k
t k t k t k t k
e e
k k
A k
A
e e
k k
A k
e A A e A k A k
dt
A d
A k A k
dt
A d
2 1
2 1 2 1
1 2
0
1 1
2
1 2
0
1 1
0
2 2
0
1 1 2 2
2
1 1 2 2
2

+ = = +
= +
Standard
methods
b
3
) Third:
If @ t=0
[A
2
]
0
=0
[A
1
]
0
= [A
1
] + [A
2
] + [A
3
] [A
3
] = [A
1
]
0
- [A
1
] - [A
2
]
| | | | ( ) | | | |
(

=
(

=
t k t k t k t k t k
e
k k
k
e
k k
k
A A e e
k k
k
e A A
2 1 2 1 1
1 2
1
1 2
2
0
1 3
1 2
1
0
1 3
1 1
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
K
1
= 1
K
2
= 100
K
1
= 1
K
2
= 0.1
A B C C B A
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
K
1
= 1
K
2
= 0.01
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
K
1
= 1
K
2
= 0.1
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
K
1
= 1
K
2
= 10
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
K
1
= 1
K
2
= 100
c) Parallel reactions:
(First order decay to different products)
A
1
A
2



A
3
k
2

k
3
| |
| | | |
| |
| |
| |
| |
1 3
3
1 2
2
1 3 1 2
1
A k
dt
A d
A k
dt
A d
A k A k
dt
A d
=
=
+ =
c
1
) First:
| |
( )| |
| |
| |
| |
| |
( ) | | | |
( )t k k
t
t
A
A
e A A dt k k
A
A d
A k k
dt
A d
3 2
0
1
0
1
0
1 1 3 2
1
1
1 3 2
1
+
= + =
+ =
} }
( )
3 2
' k k k + =
c
2
) Second:
| |
| |
( )
| |
| |
| |
( )
| |
| |
( )
( )
( )
t k k
at at
t
t k k
A
t k k
e
k k
A k
A
e
a
dt e
dt e A k A d
e A k
dt
A d
3 2
3 2
2
3 2
1
1
3 2
0
1 2
2
0
0
1 2
0
2
0
1 2
2
+
+
+

+
=
=
=
=
}
} }
[A
2
]
0
= 0
c
3
) Third:
| |
| |
( )
| |
| |
| |
( )
| |
| |
( )
( )
( )
t k k
at at
t
t k k
A
t k k
e
k k
A k
A
e
a
dt e
dt e A k A d
e A k
dt
A d
3 2
3 2
3
3 2
1
1
3 2
0
1 3
3
0
0
1 3
0
3
0
1 3
3
+
+
+

+
=
=
=
=
}
} }
[A
3
]
0
= 0
b


a
b


a
b


a
b


a
0 0.5 1 1.5 2
0
0.5
1
1
0
A1 t ( )
A2 t ( )
A3 t ( )
2 0 t
k
2
= 1, k
3
=10
0 0.5 1 1.5 2
0
0.5
1
1
0
A1 t ( )
A2 t ( )
A3 t ( )
2 0 t
k
2
= 1, k
3
=1
0 0.5 1 1.5 2
0
0.5
1
1
0
A1 t ( )
A2 t ( )
A3 t ( )
2 0 t
k
2
= 1, k
3
=0.1
A
1
A
2



A
3
k
2

k
3
d) Parallel reactions:
A
1
A
2



A
3
k
1

k
3
| |
| |
| |
| | | |
| |
| |
3 3
3
3 3 1 1
2
1 1
1
A k
dt
A d
A k A k
dt
A d
A k
dt
A d
=
+ =
=
| | | |
| | | |
| | 0
0
2
0
3 3
0
1 1
=
=
=
=
A
A A
A A
t
| | | |
( )
| | | |
( )
| |
| |
( )
| |
( )t k t k
t k
t k
e A k e A k
dt
A d
e A A
e A A
3 1
3
1
0
3 3
0
1 1
2
0
3 3
0
1 1

+ =
=
=
| |
| |
| |
( )
| |
( )
| | | | | |
( )
| | | |
( )t k t k
t
t k
t
t k
A
e A A e A A A
dt e A k dt e A k A d
3 1
3 1
2
0
3
0
3
0
1
0
1 2
0
0
3 3
0
0
1 1
0
2


+ =
+ =
} } }
0 1 2 3 4
0
0.5
1
1.5
1.311
0
A1 t ( )
A2 t ( )
A3 t ( )
4 0 t
0 1 2 3 4
0
0.5
1
1.5
2
1.963
0
A1 t ( )
A2 t ( )
A3 t ( )
4 0 t
0 1 2 3 4
0
0.5
1
1.5
2
1.982
0
A1 t ( )
A2 t ( )
A3 t ( )
4 0 t
k
1
= 1, k
3
=10 k
1
= 1, k
3
=1 k
1
= 1, k
3
=0.1
A
1
A
2



A
3
k
1

k
3
Steady-State approximation
This method is very useful
when intermediates are present
in small amount [A
i
]
| |
0 ~
dt
A d
i
If we take the case b
2
) of
Consecutive reactions
(k
1
<< k
2
)
| |
| | | |
| | | |
1
2
1
2
1 1 2 2
2
0
A
k
k
A
A k A k
dt
A d
SS
~
~ + =
| | | |
t k
SS
e A
k
k
A
1
0
1
2
1
2

~
| | | | ( )
t k
SS
e A A
1
1
0
1 3

~
A
1
A
2
A
3
k
1

k
2
A
1
A
2
A
3
k
1
K
-1
k
2
Home work!
0 2 4 6 8 10
0
0.2
0.4
0.6
0.8
1
1
0
A t ( )
A 0 ( )
B t ( )
A 0 ( )
C t ( )
A 0 ( )
10 0 t
| | | |
| | | | 0
0
0
3 0 2
0 1 1
= =
=
=
A A
A A
t
| | | | ) 1 (
1
0
1 3
t k
SS
e A A

~
The Michaelis-Menten mechanism
(Enzyme action)
+ +
S (Substrate) E (Enzyme) X
(Enzyme-Substrate
complex)
E (Enzyme)
P
1
& P
2
(Products)
True chemical
Intermediate
[ES] << 1
K
2
> k
1
| |
0 ~
dt
ES d
Another Initial condition is:
[E]
0
= [E] + [ES]
[S]
0
= [S] + [P]
| | | | | | S E ES << ~
E + S ES E + P
k
1
K
-1
K
-2
K
2
| | | |
| || | | |
| |
( )| | | || | | || |
| |
| || |
( )
| || |
( )
1 2
2
1 2
1
2 1 1 2
1 1
0

+
+
+
=
+ ~ ~
= =
k k
P E k
k k
S E k
ES
P E k S E k ES k k
dt
ES d
ES k S E k
dt
P d
dt
S d
SS
SS
| | | | | | | || |
| | | |
2 1 2 1
0 2 1 2 1
k k P k S k
E P k k S k k
dt
S d
+ + +

=

E + S ES E + P
k
1
K
-1
K
-2
K
2
Considering
[S] >> [P] @ t = 0
| | | | | | S E ES << ~
| | | | | || |
| |
| |
| | | |
| |
| |
| | S
K
v
v E k v
k
k k
K
S k
k k
E k
dt
S d
v
S k
k k S k
E S k k
dt
S d
M
S
S
M
+
= =
+
=
+
+
= =

+ +
=

1
1
0 2
1
2 1
1
2 1
0 2
1
2 1 1
0 2 1
Michaelis-Menten
constant
K
M
v
S
[S]
v
v
S
2
t ~ 0
t ~ 0
Galaxies