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Chapter 6
Chemical Kinetics
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Chemical kinetics
Chemical kinetics is the study of reaction rates, or
the changes in the concentrations of reactants or
products with time.

By studying kinetics, insights are gained to control
reaction conditions to achieve a desired outcome.

One of the main goals of chemical kinetics is to
understand the reaction mechanism.


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Reaction Rate
Reaction rate - changes in the concentrations of
reactants or products per unit time.
aA + bB cC + dD
rate =
1
a
- = -
[A]
t
1
b
[B]
t
1
c
[C]
t
= +
1
d
[D]
t
= +
Units for rate: mol L
-1
s
-1
3
In order to measure the reaction rate you need to
measure the concentration of at least one
component in the mixture at many points in time.

There are two ways of approaching this problem:

1) for reactions that are complete in a short time, it is
best to use continuous monitoring of the
concentration, or

2) for reactions that happen over a very long time,
sampling of the mixture at various times can be used.
Measuring Reaction Rate
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Spectrophotometric monitoring of a reaction.
Measurements must be
fast and reproducibly.
Conductometric monitoring of a reaction
When non-ionic reactants form ionic
products or vice versa, the change in
conductivity of the solution over time
can be used to measure the rate.
Manometric monitoring of a reaction
When a reaction results in a change in the
number of moles of gas, the change in
pressure with time corresponds to a
change in reaction rate.
N
2
O
4
(colorless) 2NO
2
(brown)
5
Average, Instantaneous and Initial reaction rates
Initial rate
average rate
average rate
Instantaneous rate
C
2
H
4
(g) + O
3
(g) C
2
H
4
O(g) + O
2
(g)
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Instantaneous, Initial and Average rate
Average rate is the change in measured concentrations
in any particular time period
linear approximation of a curve
The larger the time interval, the more the average
rate deviates from the instantaneous rate
The instantaneous rate is the change in concentration at
any one particular time/point on the curve.
determined by taking the slope of a line tangent to
the curve at that particular point
The initial rate is the slope of a line tangent to the curve
at t=0
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Because it has a nonpolluting product (water vapor),
hydrogen gas is used for fuel aboard the space shuttle
and may be used by Earth-bound engines in the near
future.
2H
2
(g) + O
2
(g) 2H
2
O(g)
(b) When [O
2
] is decreasing at 0.23 mol/L*s, at what rate is
[H
2
O] increasing?
-
1
2
[H
2
]
t
= -
[O
2
]
t
= +
[H
2
O]
t
1
2
0.23mol/L*s = +
[H
2
O]
t
1
2
; = 0.46mol/L*s
[H
2
O]
t
rate =
(a)
[O
2
]
t
- = - (b)
(a) Express the rate in terms of changes in [H
2
], [O
2
], and [H
2
O]
with time.
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The Rate Law (or rate equation) expresses the rate as a function of
reactant concentrations and temperature.

The rate of a reaction is directly proportional to the concentration of
each reactant raised to a power.

For the reaction aA + bB products the rate law would be


n and m are called the orders for each reactant. Can take the
value as integer, zero or fraction
defines how reaction rate is affected by reactant concentration.
Overall order of the reaction = m+n
k is called the rate constant, is specific for a given
reaction at a given temperature.
m n
k [B] [A] Rate=
The Rate Law
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Types of Rate Laws
Differential rate law is the one that expresses rate
dependence of rate on concentration.

Integrated rate law expresses how the concentrations
depend on time.

Once we determine experimentally either type of rate
law for a reaction, we automatically know the other one.
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Reaction order Differential rate law

Zero order

First order


Second order

k Rate =
k[B] Rate or k[A] Rate = =
2 2
k[B] Rate or k[A] Rate or k[A][B] Rate = = =
Zero, First and Second order reactions.
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Integrated Rate Laws
rate = -
[A]
t
= k [A]
rate = -
[A]
t
= k [A]
0

rate = -
[A]
t
= k [A]
2

first order rate equation
second order rate equation
zero order rate equation
ln
[A]
0
[A]
t
= kt ln [A]
0
= kt + ln [A]
t

1
[A]
t

1
[A]
0

- = kt
1
[A]
t

1
[A]
0

+ = kt
[A]
t
- [A]
0
= -kt
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rate = -
[A]
t
= k [A]
0

- [A] t = k [A]
0

[ ]
[ ]
[ ]

=
t
0
0
A
A
t d [A] k A d
0
[A]
t
- [A]
0
= - kt

OR

[A]
t
= - kt + [A]
0
Zero First Second
ln
[A]
0
[A]
t
= kt
ln [A]
t
= - kt + ln [A]
0

OR
rate = -
[A]
t
= k [A]
- [A] t = k [A]
1

[ ]
[ ]
[ ]
kt
[A]
[A]
In -
t d k A d
[A]
1
t k [A]
[A]
1
0
t
0
A
A
0
=
=
=

1
[A]
t

1
[A]
0

- = kt
1
[A]
t

1
[A]
0

+ = kt
OR
rate = -
[A]
t
= k [A]
2

- [A] t = k [A]
2

[ ]
[ ]
[ ]
kt
[A]
1
[A]
1
kt
[A]
1
[A]
1
t d k A d
[A]
1
t k [A]
[A]
1
0
0
t
0
A
A
2
2
0
= +
=
=
=

) (
) (










13
14
Second order reaction Type II
Assuming the reaction is first order in both A and B
The rate with respect to time derivative of reactant concentration is
The loss rate for the reactants is equal
(1)
(2)
Consider the case where 0
d[A]/dt = - k[A][B] = - k[A]( + [A])
d[A]
[A]( + [A])


[A]
0
[A]
= -
0
t
k dt
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This equation is applicable when [B]
0
[A]
0
The concept of half life does not apply to second order reactions of type II
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Determining the Reaction orders
can ONLY be determined experimentally.
Initial rates method.
Isolation method
Graphical method
Half life method



16
Initial Rate Method
Experiment
Initial Reactant
Concentrations (mol/L)
Initial Rate
(mol/L*s)
1
2
3
4
5
O
2
NO
1.10x10
-2
1.30x10
-2
3.21x10
-3

1.10x10
-2
3.90x10
-2
28.8x10
-3

2.20x10
-2

1.10x10
-2

3.30x10
-2

1.30x10
-2

2.60x10
-2

1.30x10
-2

6.40x10
-3

12.8x10
-3

9.60x10
-3

2NO
(g)
+ O
2(g)
2NO
2(g)
Table 16.2 Principles of General Chemistry, Silberberg, McGraw-Hill Education (Asia)
rate = k [O
2
]
m
[NO]
n

Change the initial concentration of that reactants one by one and
monitor the initial rate
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Determining Reaction Orders
Compare
experiments
1 and 2
k [O
2
]
2
m
[NO]
2
n

k [O
2
]
1
m
[NO]
1
n

=
rate
2

rate
1

=
[O
2
]
2

[O
2
]
1

m
6.40x10
-3
mol/L*s
3.21x10
-3
mol/L*s
=
1.10x10
-2
mol/L
2.20x10
-2
mol/L
m
; 2 = 2
m
m = 1
k [O
2
]
3
m
[NO]
3
n

k [O
2
]
1
m
[NO]
1
n

=
rate
3

rate
1

=
[NO]
3

[NO]
1

n
Compare
experiments
1 and 3
12.8x10
-3
mol/L*s
3.21x10
-3
mol/L*s
=
1.30x10
-2
mol/L
2.60x10
-2
mol/L
n
; 2
2
= 2
n
n = 2
rate = k [NO]
2
[O
2
]
1

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Many gaseous reactions occur in a car engine and exhaust system.
One of these is
Use the following data to determine the differential rate law.
Experiment Initial Rate(mol/L*s) Initial [NO
2
] (mol/L) Initial [CO] (mol/L)
1
2
3
0.0050
0.080
0.0050
0.10
0.10
0.40
0.10
0.10
0.20
rate = k [NO
2
]
m
[CO]
n

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0.080
0.0050
rate 2
rate 1
[NO
2
]

2

[NO
2
]

1
m
=
k [NO
2
]
m
2
[CO]
n
2

k [NO
2
]
m
1
[CO]
n
1
=
0.40
0.10
=
m
; 16 = 4
m
and m = 2
k [NO
2
]
m
3
[CO]
n
3

k [NO
2
]
m
1
[CO]
n
1
[CO]

3

[CO]

1
n
=
rate 3
rate 1
=
0.0050
0.0050
=
0.20
0.10
n
; 1 = 2
n
and n = 0
The reaction is
2nd order in NO
2
.
The reaction is
zero order in CO.
rate = k [NO
2
]
2
[CO]
0
= k [NO
2
]
2

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Isolation method
Consider
The rate law is
The reaction is performed with one reactant [A] in excess
The reaction becomes pseudo
th
order with respect to B and can be
determined by the previously mentioned method.

For , we can make [B]
0
in excess and determine in the same way as above.
Integrated rate laws and reaction order
ln[A]
t
= -kt + ln[A]
0

1/[A]
t
= kt + 1/[A]
0

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

Units of k
(t in seconds)
0
mol L
-1
s
-1

s
-1

L mol
-1
s
-1

Figure16.5 Principles of General Chemistry, Silberberg, McGraw-Hill Education (Asia)
t
[A] [A]
k
0 t

=
1
[A]
t

1
[A]
0

- = kt
ln
[A]
0
[A]
t
= kt
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Graphical determination of the reaction order
for the decomposition of N
2
O
5
.
The overall reaction order
is first order.

k = 4.82 x 10
-3
s
-1
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Reaction half-life (t
1/2
)
ln
[A]
0
[A]
t
= kt ln [A]
0
= kt + ln [A]
t

2 / 1
0
0
] [
2
1
] [
ln kt
A
A
=
2 / 1
2 ln kt =
By substituting, t = t
1/2
and [A]
t
= 1/2[A]
0


24
A plot of [N
2
O
5
] vs. time for three half-lives.
t
1/2
=
for a first-order process
ln 2
k
0.693
k
=
Figure 16.9 Principles of General Chemistry, Silberberg, McGraw-Hill Education (Asia)
1/8 [A]
0
1/2 [A]
0
1/4 [A]
0
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1
[A]
t

1
[A]
0

- = kt
1
[A]
t

1
[A]
0

+ = kt
[A]
t
- [A]
0
= - kt [A]
t
= - kt + [A]
0
Zero
Second
By substituting, t = t
1/2
and [A]
t
= 1/2[A]
0


By substituting, t = t
1/2
and [A]
t
= 1/2[A]
0


1/2[A]
0
- [A]
0
= - kt
1/2
-1/2[A]
0
= - kt
1/2
1/2[A]
0
/k = t
1/2
1/2[A]
0
x 1/k = t
1/2
t
1/2
= [A]
0
/2k
1
1/2[A]
0

1
[A]
0

- = kt
1/2
2
[A]
0

1
[A]
0

- = kt
1/2
1
k[A]
0

t
1/2
=


























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measure t
1/2
vs [A]
0


zero order: t
1/2
is proportional to [A]
0


first order: t
1/2
is independent of [A]
0

second order: t
1/2
is proportional to 1/[A]
0
Half life method to determine rate law.
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For most reactions, in order for a reaction to take place,
the reacting molecules must collide with each other.

once molecules collide they may react together or they
may not, depending on two factors

1) whether the collision has enough energy to "break the
bonds holding reactant molecules together";

2) whether the reacting molecules collide in the proper
orientation for new bonds to form.

Collision Theory of Kinetics
Takes into account the reaction rate as the result of
particles colliding with a certain frequency and
minimum energy
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The number of collisions are the product of reactant concentrations.
A
A
B
B
A
A
B
B
A
2 molecules of A
2 molecules of B
number of collisions = 4
A
A
B
B
A B
3 molecules of A
2 molecules of B
number of collisions = 6
3 molecules of A
3 molecules of B
number of collisions = 9
Why concentrations are multiplied in
the rate law
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The Arrhenius Equation

k = Ae

Ea
RT
ln k = ln A - E
a
/RT
ln
k
2

k
1

=
E
a

R
-
1
T
2

1
T
1

-
where k is the kinetic rate constant at T
E
a
is the activation energy
R is the universal gas constant
T is the Kelvin temperature
A is the collision frequency factor
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Temperature and Kinetics
REACTANTS
PRODUCTS
ACTIVATED STATE
C
o
l
l
i
s
i
o
n

E
n
e
r
g
y

C
o
l
l
i
s
i
o
n

E
n
e
r
g
y

E
a (forward)

E
a (reverse)

Activation Energy
An energy threshold that the colliding molecules must exceed
in order to react
H
H
rxn
= Ea
(fwd)
Ea
(rev)
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Graphical determination of the
activation energy
ln k = -E
a
/R (1/T) + ln A
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E
a
(kJ/mol) f (at T = 298 K)
50 1.70x10
-9

75 7.03x10
-14

100 2.90x10
-18

T f (at E
a
= 50 kJ/mol)
25
0
C(298K) 1.70x10
-9

35
0
C(308K) 3.29x10
-9

45
0
C(318K) 6.12x10
-9

f = Fraction of
collisions
Smaller Ea
or higher T
Larger k
Higher rate
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The effect of temperature on the distribution
of collision energies
35
The Arrhenius Equation : k = A e
-Ea/RT

A : Frequency factor or Arrhenius pre-exponential factor
A = pZ
Collision frequency Orientation probability factor
The orientation probability factor p is
Specific for each reaction
Related to the structural
complexity of the colliding particles
Ratio of effectively oriented
collisions to all possible collisions
How molecular structure affects rate
36
Collision
frequency is
controlled by
concentration
and
temperature
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Transition State Theory
Molecular nature of the activated complex
Transition state or activated complex
is formed only if the molecules collide in an
effective orientation and with energy equal
to or greater than the E
a.


Every reaction (and every step in an overall
reaction) goes through its own transition
state, from which it can continue in either
direction.



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Reaction energy diagram for the reaction of CH
3
Br and OH
-
.
Visualizing the Transition State
38
Reaction energy diagrams and possible transition states for 3 reactions
2NOCl
(g)
2NO
(g)
+ Cl
2 (g)

NO
(g)
+ O
3 (g)
NO
2(g)
+ O
2 (g)

2ClO
(g)
Cl
2(g)
+ O
2 (g)
39
Conclusions
Collision Theory Reactant particles
must collide with the right orientation and
enough energy in order to react

Transition State Theory The reactant
species forms an unstable, high energy
transition state, which either forms
product(s) or reverts to reactant(s).
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41
Sequential First order Reactions
I = intermediate
The differential rate expressions are
To determine the concentration of each species as a function of time,
we integrate them
At t = 0,
The expression for [A] from the integrated rate law-first order expression,
(1)
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42
Substitute for [A] in the differential rate expression for I
When solved for [I] we get
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43
k
A
= 2k
I
k
A
= 8k
I
k
A
= 0.25k
I
Inference : If the intermediate undergoes decay at a faster rate
than the rate at which it is being formed then the intermediate
concentration will be small
When is the maximum [I] reached?
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Rate determining step in sequential reactions
If k
A
>> k
I
If k
I
>> k
A
In each case only the rate constant
of the slow step appears in the rate
equation.
The rate determining step in
sequential reactions is the slowest
step .
It determines the rate of the
product formation
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Parallel reactions
In this reaction reactant A can form one of the two products B and C.
The differential rate expressions for reactant and product are
k
B
= 2k
C
= 0.1s
-1
46
Assume [A]
0
> 0 and [B]
0
= [C]
0
= 0, After integration:
What will the expressions when k
B
<< k
C
and k
B
>> k
C
?

Which step is the rate determining step in each case?
47
Reversible reactions
Differential rate expression for each species
Assume [A]
0
> 0 and [B]
0
=0, after integration
A and B reach equilibrium after
a long time
Reaction Mechanism
Any chemical reaction can be broken down into a set of
elementary reactions/steps.

Describing the series of steps that occur to produce the overall
observed reaction is called a reaction mechanism

Chemists propose a reaction mechanism to explain how a
particular reaction might occur and then test the mechanism.

The rate law for elementary reaction can be deduced from the
reaction stoichiometry [reaction order equals molecularity]



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Reaction Mechanism An Example
Overall reaction:
H
2(g)
+ 2 ICl
(g)
2 HCl
(g)
+ I
2(g)


Proposed mechanism:
1) H
2(g)
+ ICl
(g)
HCl
(g)
+ HI
(g)

2) HI
(g)
+ ICl
(g)
HCl
(g)
+ I
2(g)


the steps in this mechanism are elementary steps, meaning
that they cannot be broken down into simpler steps and that
the molecules actually interact directly in this manner without
any other steps
materials that are products in an early step, but then a
reactant in a later step are called intermediates.


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Reaction intermediates
A substance that is formed and used up

Do not appear in the overall equation

Unstable relative to reactants or products but more stable than
transition states

Reactive intermediates are usually short lived and are very seldom
isolated.

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Molecularity
the number of reactant particles in an elementary
step is called its molecularity

a unimolecular step involves 1 reactant particle

a bimolecular step involves 2 reactant particles
though they may be the same kind of particle.

a termolecular step involves 3 reactant particles
though these are exceedingly rare in elementary
steps
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Rate Laws for General Elementary Steps
Elementary Step Molecularity Rate Law
A product
2A product
A + B product
2A + B product
Unimolecular
Bimolecular
Bimolecular
Termolecular
Rate = k [A]
Rate = k [A]
2

Rate = k [A][B]
Rate = k [A]
2
[B]
Reaction order equals molecularity
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PLAN:
SOLUTION:
Determining Molecularity and Rate Laws
for Elementary Steps
PROBLEM: The following two reactions are proposed as elementary steps
in the mechanism of an overall reaction:
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
(2) NO
2
Cl(g) + Cl

(g) NO
2
(g) + Cl
2
(g)
(a) Write the overall balanced equation.
(b) Determine the molecularity of each step.
(a) The overall equation is the sum of the steps.
(b) The molecularity is the sum of the reactant particles in the step.
2NO
2
Cl(g) 2NO
2
(g) + Cl
2
(g)
(c) Write the rate law for each step.
rate
2
= k
2
[NO
2
Cl][Cl]
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
(2) NO
2
Cl(g) + Cl

(g) NO
2
(g) + Cl
2
(g)
(a)
Step(1) is unimolecular.
Step(2) is bimolecular.
(b)
rate
1
= k
1
[NO
2
Cl] (c)
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
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The Rate-Determining Step of a Reaction Mechanism
The overall rate of a reaction is related to the rate of the
slowest, or rate-determining step
Example : 2 ICl + H
2
2 HCl + I
2

Rate = k[ICl][H
2
] rate-determining step

Proposed mechanism:
Step 1: ICl + H
2
HCl + HI slow..(1)

Step 2: HI + ICl HCl + I
2
fast....(2)

Overall: 2ICl + H
2
2HCl + I
2
.... (1) + (2)

Step 1 is the rate-determining step = slow step

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Example :

Given that the decomposition of 2N
2
O
5
is a first order
reaction, propose a possible mechanism for the
reaction

2N
2
O
5
4NO
2
+ O
2


Rate = k[N
2
O
5
]
Mechanism:

N
2
O
5
NO
2
+ NO
3
(slow, rate determining)


N
2
O
5
+ NO
3
3NO
2
+ O
2


2N
2
O
5
4NO
2
+ O
2


slow
fast
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Rate Laws for Overall Reactions
NO
3
(g) + CO(g) NO
2
(g) + CO
2
(g)
NO
2
(g) + NO
2
(g) NO(g) + NO
3
(g)
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
fast step
overall reaction
slow step
Based on the slow step: rate = k
1
[NO
2
]
2

k
2

k
1

Initial Slow Step
56 CM1502 2013-14
Rate Laws for Overall Reactions
N
2
O(g) + H
2
(g) N
2
(g) + H
2
O(g)
2NO(g) + 2H
2
(g) N
2
(g) + 2H
2
O(g)
slow step
overall reaction
fast step, reversible
Based on the slow step: rate = k
2
[N
2
O
2
][H
2
]
k
3

k
-1

Initial Fast Step
2NO(g) N
2
O
2
(g)
k
1

N
2
O
2
(g) + H
2
(g) N
2
O(g) + H
2
O(g)
k
2

fast step
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The rate law of the slowest step determines how fast the overall
reaction occurs.
Rate Laws for Overall Reactions
rate = k
2
[N
2
O
2
][H
2
]
intermediate
First step: Rate
reverse
= k
-1
[N
2
O
2
] Rate
forward
= k
1
[NO]
2

k
1
[NO]
2
= k
-1
[N
2
O
2
]
[NO]
2
[N
2
O
2
] =
k
-1

k
1

Slow step: rate = k
2
[N
2
O
2
][H
2
] rate = k
2

[NO]
2
[H
2
]
k
-1

k
1



58 CM1502 2013-14
59
The steady state approximation
I
1
and I
2
are intermediates
To determine the concentration of the species we have two ways.
Numerical method
Steady state approximation
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60
Concentrations determined
by numerical evaluation
Where k
A
=0.02s
-1
and k
1
=k
2
=0.2 s
-1
I
1
and I
2
undergo very little change with time
This is called steady state approximation.
[P]ss: curve corresponding
to steady state approximation
CM1502 2013-14 61
Within steady state approximation, [P] is predicted with
first order decay of A




Steady state approximation is valid when
k
1
>> k
A
k
2
>> k
A
Rate Laws for Overall Reactions
Procedure for Studying Reaction Mechanisms
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Proposed
mechanism must
add up to the
overall reaction,
be physically
reasonable, and
conform to the
overall rate law.
Catalysts
A catalyzed reaction yields the products more quickly,
but DOES NOT yield more product than the
uncatalyzed reaction.

A catalyst increases the reaction rate by providing a
different mechanism, through which the activation
energy is lower.

A catalyst increases the rate of the forward AND the
reverse reactions.


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Reaction energy diagram of a catalyzed and an uncatalyzed
process.
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CM1502 2013-14 65
Enzyme kinetics
Michaelis Menten
rate law
Where
K
m
signifies the rate constants of ES dissociation over
the rate constants of ES formation.
Summary
1. Measuring Reaction Rates
2. Rate Expressions
3. The Rate Law and Its Components
4. k dependence on T
5. Collision Theory
6. Reaction Mechanism
7. Use of catalysts
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