Ramon Lu

Gerico Alforja
Lorenzo Aramil

Chemical Kinetics
Chemical kinetics - speed or rate at which a reaction
occurs
How are rates of reactions affected by
Reactant concentration?
Temperature?
Reactant states?
Catalysts?
The Instantaneous Reaction Rate
Consider the following reaction
A + B C
Define the instantaneous rate of consumption of
reactant A, v
A


| |
dt
A d
A
= v
Reaction Rates and Reaction
Stoichiometry
Look at the reaction
O
3
(g) + NO(g) NO
2
(g) + O
2
(g)
| |
dt
]
O
d[
+ =
dt
]
NO
d[
+ =
dt
d[NO]
- =
dt
O
d
- = rate
2 2 3
Another Example
2 NOCl (g) 2 NO + 1 Cl
2
(g)


| |

dt
d[Cl
+ =
dt
d[NO]
2
1
=
dt
NOCl d
2
1
- = rate
2
]
+
WHY? 2 moles of NOCl disappear
for every 1 mole Cl
2
formed.

The General Case
a A + b B c C + d D
rate = -1 d[A] = -1 d[B] = +1 d[C] = +1 d[D]
a dt b dt c dt d dt
Why do we define our rate in this way?
removes ambiguity in the measurement of reaction rates
Obtain a single rate for the entire equation, not just for
the change in a single reactant or product.
Alternative Definition of the Rate
Rate of conversion related to the
advancement of the reaction, .
dt
d
V
1
= reaction of rate

V = solution volume
An Example
Examine the following reaction
2 N
2
O
5
(g) 4 NO
2
(g) + O
2
(g)

N
2
O
5
NO
2
O
2
Initial n

0 0
Change -2 +4 +
Final n

- 2 4
The N
2
O
5
Decomposition
| | | |
| |
| |

dt
V d
=
dt
] d[O
dt
V d
4 =
dt
] d[NO

dt
V d
2 - =
dt
O N d
2
2
5 2

+
dt
d
V
1
= reaction of rate

Note constant
volume system
The Rate Law
Relates rate of the reaction to the
reactant concentrations and rate
constant
For a general reaction
a A + b B + c C d D + e E
z y x
[C] [B] k[A]
dt
d
V
1
v Rate = = =

Rate Laws (Contd)
The only way that we can determine the
superscripts (x, y, and z) for a non-
elementary chemical reaction is by
experimentation.
Use the isolation method (see first year
textbooks).
For a general reaction
E x + y + z = reaction order
e.g. X = 1; Y = 1; Z = 0
2nd order reaction (x + y + z = 2)
X = 0; Y = 0; Z = 1 (1st order reaction)
X = 2; Y = 0; Z = 0 (2nd order)
Rate Laws for Multistep Processes
Chemical reactions generally proceed via
a large number of elementary steps - the
reaction mechanism
The slowest elementary step the rate
determining step (rds).
An Example Reaction Mechanism
O atoms are intermediates in the above reaction
sequence.
Intermediates generally small, indeterminate
concentrations.

+
+
1
1
2
3 2
3 2
O O O
O O 2O
k
k
k
Integrated Rate Laws
The rate law gives us information about
how the concentration of the reactant
varies with time
How much reactant remains after
specified period of time? Use the
integrated rate laws.
First Order Reaction
A product
Rate = v = - d[A]/d t = k[A]
How does the concentration of the
reactant depend on time?
kt
A
A
o
=
|
|
.
|

\
|
ln
k has units of s
-1

The Half-life of a First Order
Reaction
For a first order reaction, the half-life t
1/2
is calculated as follows.
k
693 0
t
2 1
.
/
=
Radioactive Decay
Radioactive Samples decay according to first
order kinetics.
This is the half-life of samples containing
e.g.
14
C ,
239
Pu,
99
Tc.
Example
|
0
1
14 14
N C

+
Second Order Reaction
A products v = k[A]
2
A + B products v = k[A][B]
Case 1 is 2
nd
order in A
Case 2 is 1
st
order in A and B and 2
nd
order overall
The Dependence of Concentration
on Time
For a second order process where v =
k[A]
2

| | | |
kt
A
1
A
1
o
+ =
Half-life for This Second Order
Reaction.
[A] at t = t = [A]
0






0
2 1
2 1
o 0
A k
1
=
t
or
kt
+
A
1
=
/2 A
1
] [
] [ ] [
/
/
Other Second Order Reactions
Examine the Case 2 from above
A + B products v = k[A][B]
| |
| |
| |
| |
| | | | ( )
o o
o
o
A B kt
A
A
B
B
=

ln
A Pseudo-first Order Reaction
Example hydration of methyl iodide
CH
3
I(aq) + H
2
O(l) CH
3
OH(aq) + H
+
(aq) +
I
-
(aq)
Rate = k [CH
3
I] [H
2
O]
Since we carry out the reaction in aqueous
solution
[H
2
O] >>>> [CH
3
I] [H
2
O] doesnt change
by a lot
Pseudo-first Order (contd)
Since the concentration of H
2
O is
essentially constant
v = k [CH
3
I] [constant]
= k` [CH
3
I] where k` = k [H
2
O]
The reaction is pseudo first order since it
appears to be first order, but it is actually a
second order process.
Sequential First Order Reactions

Suppose we have two first order reactions
occurring in sequence.





v k A
v k A
b a
c b
A B
B C
= (

= (

What is Our Intermediate?
B is an intermediate in the above reaction
sequence.
Clearly B is formed in the first elementary step of
the reaction mechanism and consumed in the final
step.
The Concentration Dependencies
of the Species
The amounts of the reactants are related to the
reaction rates as follows.
( (

= = ( (

(

= ( (

;
a b
a b
d A d C
k A k B
dt dt
d B
k A k B
dt
Sequential Reactions (3)
For a set of initial conditions [A]
o
0, and [B]
o
=
[C]
o
=0 mol/L.




{ }
k
k
A A
A
k A k B
a
a
t
O
t
a b
O
e
d
e
dt

= ( (

(

=
( (

=
Sequential Reactions (4)
The concentration of the intermediate can be
written

{ }
k k
k
B A
k k
a b
t t
a
O
b a
e e

= ( (

Sequential Reactions (5)

k k
k k
C 1 A
k k
b a
t t
a b
O
b a
e e

| |

= + ( (
|

|

\ .


o
o
Note A A B C
Hence C A A B
= + + ( ( ( (

= ( ( ( (

The Rate Determining Step of the
Reaction
What happens if one of the steps in the reaction is
much slower than the other reaction step?
( )
k k
k
k k
lim lim 1 A
k k
1 A
b a
b b
a
t t
a b
O
k k
b a
t
O
e e
C
e

| |

= + ( (
| `

|

\ .
)
= (

Note assuming k
a
<<< k
b

The Rate Determining Step of the
Reaction (2)
If k
b
<<< k
a

( )
k k
k
k k
lim lim 1 A
k k
1 A
b a
a a
b
t t
a b
O
k k
b a
t
O
e e
C
e

| |

= + ( (
| `

|

\ .
)
= (

Temperature Dependence of
Reaction Rates
Reaction rates generally increase with increasing
temperature.
Arrhenius Equation

RT
E
a
e A k

=
A = pre-exponential factor
E
a
= the activation energy
Reactions Approaching Equilibrium
Examine the concentration profiles for the
following simple process.
A B
Time
C
o
n
c
e
n
t
r
a
t
i
o
n
A
B
Approaching Equilibrium
Calculate the amounts of A and B at
equilibrium.
| | | |
k
v
V
A A
eq A
o eq
,
=
|
.
|

\
|
=

| |
/
,
k
v
V
B
eq B
eq
=
|
.
|

\
|
=

The Equilibrium Condition
At equilibrium, v
A,eq
= v
B,eq
.

| | | |
eq B eq eq A eq
v B k v A k
,
/
,
= = =
| |
| |
K
A
B
k
k
eq
eq
= =
/
Elementary steps and the
Molecularity
Kinetics of the elementary step depends only
on the number of reactant molecules in that
step!
Molecularity the number of reactant
molecules that participate in elementary
steps
The Kinetics of Elementary Steps
For the elementary step


unimolecular step
For elementary steps involving more than one
reactant


a bimolecular step

| | A k v products A =
| || | B A k v products B A = +
The Kinetics of Elementary Steps
For the elementary step


unimolecular step
For elementary steps involving more than one
reactant


a bimolecular step

| | A k v products A =
| || | B A k v products B A = +
For the step


a termolecular (three molecule) step.
Termolecular (and higher) steps are not
that common in reaction mechanisms.
| | | | B A k v products B A 2
2
= +
The Steady-State Approximation
Examine the following simple reaction mechanism
| | B k v
2 p
=
Rate of product formation, v
p
, is proportional
to the concentration of an intermediate.


1 2
1
k k
k
A B P

Applying the Steady State

Approximation (SSA)
Look for the intermediate in the mechanism.
Step 1 B is produced.
Reverse of Step 1 B is consumed.
Step 2 B is consumed.
| |
| | | | | | B k B k A k
dt
B d
2 1 1
=

The SSA (Contd)
The SSA applied to the intermediate B.
| |
| | | | | |
| |
| |
2 1
1
2 1 1
k k
A k
B
B k B k A k
0
dt
B d
+
=
+ =
=

SSA The Final Step

Substitute the expression for the concentration of
B into the rate law v
p
.
| |
| |
| |
| | A
k k
k k
dt
P d
B k
dt
P d
2 1
1 2
2
+
=
=

Competing Reactions

Imagine a reaction with a competing side reaction.





= (

= (

v k A
v k A
b a
c b
A B
A C
The Reaction Yield

We can calculate the amount of material
produced from the competing reactions.



J
n
n
k
k
u =

k
J
= the rate constant for the reaction J.

Activated Complex Theory
Consider the following bimolecular reaction

k
A B C +

Presume that the reaction proceeds through the
transition state?
1
1
k
k
k
A B AB P

+

The Activated Complex
The species temporarily formed by the reactant
molecules the activated complex.
A small fraction of molecules usually have the
required kinetic energy to get to the transition state
The concentration of the activated complex is
extremely small.
Transition State Theory (TST)
TST pictures the bi-molecular reaction proceeding
through the activated complex in a rapid-pre-
equilibrium.
1
1
k
k
k
A B AB P
d P
k AB
dt

+
(

(
=

TST (II)
From the thermodynamic equilibrium constant for the
formation of AB

;
A B
AB
A B
A B
AB
p
K
p p
p RT A p RT B
p RT AB
RT
AB K
P
=
= = ( (

(
=

(
= ( (


TST (IV)
Assume that we can obtain the Gibbs energy of
activation from K

.
2
ln
G
B
RT
o
G RT K
k T RT
k e
h P
A
A =
=
The Eyring Equation!
TST (V)
Hence, substituting for the Gibbs energy of activation
in terms of the enthalpy and entropy of activation.
2
S H
B
RT R
o
G H T S
k T RT
k e e
h P
A A
A = A A
=
TST (VI)
Expressing the enthalpy of activation in terms of the
activation energy.
2 bimolcular gas phasereaction
unimolecular gas phase
or solutionreaction
a
a
H E RT
H E RT
A =
A =
TST (VII)
The final result for a bimolecular gas phase reaction.
2
2
a
E
S
B
RT R
o
k T RT
k e e e
h P

A
=
2
2
2
a a
E E
S
B
RT R RT
o
S
B
R
o
k T RT
k Ae e e
h P
k T RT
A e
h P

A
+
A
+
= =
=
TST (VIII)
The final result for a unimolecular gas phase reaction
(or any solution reaction).
a
E
S
B
RT R
r
o
k T RT
k e e e
h P

A
=
1
1
a a
E E
S
B
RT R RT
r
o
S
B
R
o
k T RT
k Ae e e
h P
k T RT
A e
h P

A
+
A
+
= =
=