Chapter five

Chemical kinetics
Introduction

 Chemical kinetics is the branch of physical chemistry which deals with a study of
 The speed ( rate) of chemical reactions and rate laws.
 The factors as temperature, concentration and catalyst that influence the
rate of a reaction.
 The mechanism or the sequence of steps by which a reaction occurs.

1
 The rates of chemical reactions
 The rate of reaction i.e. the velocity of a reaction is the amount of a chemical
change occurring per unit time.
 The rate is generally expressed as the decrease in concentration of a reactant
or as the increase in concentration of the product.
 If C the concentration of a reactant at any time t is, the rate is dC/ dt or if the
concentration of a product be x at any time t, the rate would be dx/dt..
Let A →B
Rate of reaction = rate of disappearcnce of A
= rate of appearnce of B
Or rate = -d[A] / dt
= d[B] / dt
 The time is usually expressed in seconds.
 The rate will have units of concentration divided by time.
Hence mole/litre sec or mol l-1 s-1.
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 Cont…
Reaction Rate in terms of stoichiometry

For the reaction:

 The rate of reaction is always positive.

 The rate of chemical reaction decreases as the reaction proceeds.

3
 Cont…
Factors affecting rate of a reaction
The rate of a chemical reaction depends on the following things
(1) Nature of reactants
(i) Physical state of reactants: This has considerable effect over rate of reaction

(ii) Physical size of the reactants: Among the solids, rate increases with decrease in
particle size of the solid
(iii) Chemical nature of the reactants
(a) Reactions involving polar and ionic substances including the proton transfer
reactions are usually very fast. On the other hand, the reaction in which bonds
is rearranged, or electrons transferred are slow.
(b) Oxidation-reduction reactions, which involve transfer of electrons, are also slow as
compared to the ionic substance.
(c) Substitution reactions are relatively much slower. 4
 Cont…
2) Effect of temperature: The rate of chemical reaction generally increases on
increasing the temperature. The rate of a reaction becomes almost double or tripled
for every 10oC rise in temperature.
3) Concentration of reactants: The rate of a chemical reaction is directly
proportional to the concentration of the reactants means rate of reaction
decreases with decrease in concentration.
4) Presence of catalyst: The function of a catalyst is to lower down the activation
energy. The greater the decrease in the activation energy caused by the catalyst,
higher will be the reaction rate

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 Cont…
Rate laws or Rate equation
• For a reaction
2A + B → products
 The rate of reaction is directly proportional to the reactant concentrations,
each concentration being raised to some power
 Rate equations can only be determined experimentally and cannot be found
from the stoichiometric equations
Rate of reaction = k [A]m [B]n
[A] and [B] = concentrations of reactants
m and n = orders of the reaction
 All of the reactant concentrations will have an order of 0, 1 or 2, depending on
the effect that they have on the rate of the reaction
 The products are never involved in the rate equation, as they have no effect on
the rate of the reaction
6
 Cont…
Order of a reaction
It is defined as the sum of powers of concentrations in the rate law
• Let us consider the example of a reaction
rate = k [A]m [B]n (1)
• The order of such a reaction is (m + n)
• It can also defined with respect to a single reactant.
• Thus the reaction w.r.to A is m and w.r.to B it is n.
 The overall order of reaction is the sum of the powers of the reactants in a rate
equation
m + n = 1, it is first order reaction
m + n = 2, it is second order reaction
m + n = 3, it is third order reaction

7
 Cont…
For example, in the following rate equation, the reaction is:
Rate = k [NO]2 [H2]
Second-order with respect to NO
First-order with respect to H2
Third-order overall (2 + 1)
• When the order of reaction of a reactant is 0, this means that it has no effect on
the rate of the reaction and therefore is not included in the rate equation at all
• When the order of reaction of a reactant is 1, the rate is directly proportional to
the concentration of that reactant
• When the order of reaction of a reactant is 2, the rate is directly proportional to
the square of the concentration of that reactant

8
 Cont…
Example
 For a hypothetical reaction, A B, what happens to rate of the reaction for zero order,
first order, second order and third order if the concentration doubled and tripled?
Solution
 For zero order order, i.e Rate = k[A]0 = k, rate independent on the concentration of
reactant.
 For first order, rate1 = k[A]1
 i) [A]2 = 2[A]1 ii) [A]2 = 3[A]1
rate2 = k[A]2 rate2 = k [A]2
rate2 = k[2A]1 rate2 = k[3A]1
rate2 = 2k[A]1 rate2 = 3k[A]1
rate2 = 2 rate1 rate2 = 3rate1
 For first order reaction, if the concentration of a reactant is doubled, the rate is also
doubled and the concentration of a reactant is tripled , the rate is also tripled.

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 Cont…
 For second order reaction, rate1 = k[A]21
i) [A]2 = 2[A]1 ii) [A]2 = 3[A]1
rate2 = k[A]22 rate2 = k[A]22
rate2 = K[2A]21 rate2 = K[3A]21
rate2 = 4k[A]21 rate2 = 9k[A]21
Rate2 = 4rate1 Rate2 = 9rate1
 For second order reaction, if the concentration of a reactant is doubled, the rate is also
quadruples and the concentration of a reactant is tripled , the rate is increase by 9 folds.
 For third order reaction, rate1 = k[A]31
i) [A]2 = 2[A]1 ii) [A]2 = 3[A]1
rate2 = k[A]32 rate2 = k[A]32
rate2 = K[2A]31 rate2 = K[3A]31
rate2 = 8k[A]31 rate2 = 27k[A]31
Rate2 = 8rate1 Rate2 = 27rate1
 For third order reaction, if the concentration of a reactant is doubled, the rate is
increased by 8 folds and the concentration of a reactant is tripled , the rate is increase
by 27 folds.

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 Cont…
Molecularity of a reaction
 Molecularity is the sum of the number of molecules of reactants involved in the
balanced chemical equation.
 The reaction is said to be unimolecular, bimolecular, termolecular according to
one, two, or three molecules are involved in the process of a chemical change.
 The term unimolecular was used for all first order reactions, the term
bimolecular for 2nd order reactions etc.

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 Cont…
 Molecularity of a complete reaction has no significance and overall kinetics of
the reaction depends upon the rate determining step.
 Slowest step is the rate-determining step.
 If reaction is in the form of reaction mechanism then the order is determined
by the slowest step of mechanism.

 Molecularity of a reaction is derived from the mechanism of the given reaction.

Molecularity can not be greater than three because more than three molecules may not
mutually collide with each other.
 Molecularity of a reaction can't be zero, negative or fractional. order of a
reaction may be zero, negative, positive or in fraction and greater than three. Infinite
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and imaginary values are not possible
 Cont…
Integrated rate law
Zero order reactions
 In a zero order reaction, rate is independent of the concentration of the reactions.
 Let us consider a zero order reaction type
A→ products

𝑑[𝐴] = −𝑘𝑑t
 Now we can integrate both sides over the desired interval:

([𝐴]0 and 𝑡0 are initial conditions, whereas [𝐴] refers to the concentration after a time 𝑡 has
passed)

We consider (actually define) 𝑡0 = 0, and so the equation can take the form:

[𝐴] 𝑣𝑠 t

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 Cont…
First order reactions
 Let us consider a first order reaction
A→ products

Now we can integrate both sides over the desired interval:

We consider 𝑡0 = 0, and the equation can take the form:

ln[𝐴] 𝑣𝑠 t

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 Cont...
Example
Sulfuryl chloride, SO2Cl2, decomposes when heated:

In an experiment, the initial concentration of SO2Cl2 was 0.0248 M

The Rate Constant is 2.2 x10 -5 s-1. The Reaction is first order.
What is the concentration of SO2Cl2 after 2.5 hours?

Take antilogarithms of both sides;

15
 Cont...
Example 2:
Cyclobutane, C4H8 decomposes, when heated to give ethylene:

The reaction is first order. In an experiment, the initial concentration of C 4H8 was
0.00150 M. After heating at 450oC for 455 seconds, this was reduced to 0.00119 M.
What was the concentration of C 4H8 after a total of 827 seconds?

a) Calculate rate constant (k) for the reaction:

b) Calculate concentration of C4H8at 827 s:

Taking the antilog of both sides:

Substituting [C4H8]0
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 Cont...
Second order reactions
Let us take a second order reaction type
2A → products

If 𝑡0 = 0, then: 1/ [𝐴] 𝑣𝑠 𝑡,

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 Cont...
Example:
For the reaction
At 330 K: k = 0.775 M –1 s–1 [A] 0 = 0.0030 M [A] 645 = ?

[A]t = 0.0012 M

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 Cont...

 If a reaction takes place for which only one reactant is involved, a general rate
law can be written as

n≠1

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 Cont...
Units of rate constant
The units of rate constant for different orders of reactions are different.
Units of Zero order rate constant
k = d[A] / dt = mol/litre x 1/time
= mol l-1 time-1
Units of first order rate constant
The rate constant of a first order reaction is given by
k = (2.303/t) x log [A]0/[A]t
= time-1
Units of Second order rate constant
The rate constant of a second order reaction is given by
k = 1/t x (x/[A]0([A]0 -x)))
= concentration/ (concentration x concentration) x (1/time)
= (1/concentration) x (1/time)
= (1/mole litre-1) x (1/time)
= mol-1 l time-1
Thus the units of k for second order reactions are mol-1 l time-1
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 Cont...
Units of third order rate constant
The rate constant of a third order reaction is given by
k = 1/t x (x(2a-x)/(2a2(a-x)2))
= (concentration x concentration)/ (concentration x
concentration)2 x (1/time)
= 1/concentration)2 x (1/time)
= 1/(mole litre-1)2 x (1/time)
= mol-2 l2 time-1
Thus the units of k for third order reactions are mol-2 l2 time-1

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 Cont...
Half life a reaction
 Half-life is the time it takes for the reactant concentration to decrease to one-half
of its initial value.
 It is represented by the symbol t1/2 or t0.5.

Figure First-order half-life.

Concentration of a reactant A as
a function of time for a first-
order
reaction. The concentration falls
from its initial value, [A] , to [A]
/2 after one half-life,
to [A] /4 after a second half-life,
to [A] /8 after a third half-life,
and so on. For a
first-order reaction, each half-
life represents an equal amount
of time. 22
 Cont...
Calculation of Half life of a first order reaction
The integrated rate equation for a first order reaction can be stated as
k = (2.303/t) x log [A]0/[A]
where [A]0 is initial concentration and [A] is concentration at any time t.
Half life is time when initial concentration is reduced to half
[A] = 1/2[A]0
Substituting values in the integrated equation, we have
k = (2.303/t1/2) x log [A]0/ 1/2[A]0
= 2.303/t1/2 x log 2
Or t1/2 = 2.303/k x log2
= 2.303/k x 0.3010
t1/2 = 0.693/k
It is clear that
• Half life for a first order reaction is independent of the initial concentration
• It is inversely proportional to the rate constant.

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 Cont...
Example:
Dinitrogen pentoxide, decomposes when heated in carbon tetrachloride solvent:

The rate law is first order in N2O5 with a rate constant of 6.2x10 –4 min–1
(a) What is the half-life for this reaction?

Example
The half-life of a substance in a first order reaction is 15 minutes. Calculate the rate
constant.
Solution
For a first order reaction

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 Cont…
Half-life for a Second order Reaction
Half-life for a Second order Reaction
For the simple second order reaction 2A Products, the integrated rate equation is
1 1 where [A]o is the initial concentration and [A] is the concentration
kt  
[ A] [ A]o when time t has elapsed. When one half life has elapsed

kt 1 
1

1 2 1
1
[ A]  [ A]o and we have 1
Or kt 1  
[ A] [ A]o
2
2 2 [ A] [ A]o
2
t1
Solving for 2 we find that
1
t1 
2 k[ A]o

As in case of a first order reaction, half-life for a second order reaction is inversely
proportional to rate constant k. While half-life of a first order reaction is
independent of initial concentration, half-life of a second order reaction depends
on initial concentration. This fact can be used to distinguish between a first order
and a second order reaction.
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 Cont…
Summary Of Kinetics Equations

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 Cont…
Pseudo order reactions
 A reaction in which one of the reactants is present in a large excess shows an
order different from the actual order.
 The experimental order which is not the actual one is called as pseudo order.
 Since for elementary reactions molecularity and order are identical.
Let us consider
A + B → products
In which the reactant B is resent in a large excess.
Since it is an elementary reaction, its rate law can be written as
Rate = k [A] [B]
As B is present in large excess, its concentration remains constant.
Thus the rate law can be written as
Rate = k’ [A]
Where the new rate constant k’ = k [B].. Thus the actual order of the reaction is
second order but in practice it will be first order
Therefore the reaction is said to be pseudo first order.

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 The Kinetics of Complex Reaction
1. Reversible or Opposing Reactions
2. Parallel reaction
3. Consecutive reaction
4. Chain reaction

 The reactions in which the final product is formed through one or more intermediate
steps are called consecutive reactions. In such reactions the product formed in one of the
elementary reactions acts as the reactant for some other elementary reaction
K1 K2
A B C
 In these reactions the reacting substance follows two or more paths to give two or more
products.. The reaction in which the maximum yield of the products is obtained is called
the main or major reaction while the other reaction (or reactions) are called side or parallel
K1
reactions. For example, B

C
K2
 If k1> k2 the reaction A → B will be the major reaction and A → C will be the side or
parallel reaction

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 Cont…
Reversible or Opposing Reactions
In reversible or opposing reactions the products formed also react to give back the
reactants.
Initially, the rate of forward reaction is very large which decreases with passage of
time and the rate of backward or reverse reaction is zero which increases with
passage of item. A stage is reached when two rates become equal. This situation is
called the chemical equilibrium. It is dynamic in nature i.e., all the species are
reaching at the rate at which they are being formed. A reaction of this type may be
kf
represented as A B
kb
Initial concentration [A]o 0
Concentration after time t [A] [B]
Where kf and kb are the rate constants of the forward and backward reactions respectively
The overall rate of reaction is given by
Rate of Reaction= Rate of forward reaction–Rate of backward reaction 29
 Cont…
d [ A] d [ B] (i)
  k f [ A]  kb [ B]
dt dt
If [A]0 is the initial concentration of A and x moles of it have reacted in time t
Then [A]t=[A]o – x
and [B]= x
Substituting these in equation (i), we get
dx
 k f ([ A]o  x)  kb x
dt (ii)

dx
At equilibrium 0
dt
Hence k f ([ A]o  xeq )  kb xeq
Where xeq is the concentration of A that has reacted into B at equilibrium. From
equation (iii)we have
 [ A]o  xeq 
kb  k f  
 xeq
(iii)
 
30
 Cont…
Substituting the value of kb in equation (ii), we get
dx  [ A]o  xeq 
 k f ([ A]o  x)  k f   x
dt  xeq
 
Integrating this equation between the limits t = 0, x = 0 and t = t, x = xeq , we have
x t
dx [ A]o
0 xeq  x f xeq 0 dt
 k
xeq [ A]o t
[ A]o t ln  kf
  ln( xeq  x)  ln xeq  k f Or xeq  x xeq
xeq

From this equation we can find the value of kf from the quantities [A]o , xeq and x
at time t. All these quantities can be measured easily. From the value of kf the
value of kb can be calculated by using the relation.

 [ A]o  xeq 
kb  k f  
 xeq 
  31
Cont…

k=k1+k2

32
Cont…

The soln to the diff. eqn is

[B]=

33
Cont…

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 Cont…
steady-state approximation

[B] builds up to a very small

concentration and remains
relatively constant during the
course of the reaction

approximation d[B]/dt = 0,
equate the rate eqn associated
with this intermediate to zero

This procedure is called

steady-state approximation
It greatly simplifys the eqn
associated with a particular
kinetic model

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 Cont…
Chain reactions
Reactants are converted to one or more of reactive intermediates (usually radicals).
The intermediates further react to give products.

Steps
•Initiation: free radicals are formed
•Propagation: free radicals attack other molecules producing products and free
radicals.
•Inhibition: free radicals attack the products.
•Termination: free radicals combine to give normal molecules.

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 Cont…

Example: H2 + Br2 2HBr

Suggested mechanism
Initiation

Propagation

Inhibition

Termination

d [ HBr ] k[ H 2 ][ Br2 ]1 2
Experimental rate law  '
dt 1  [ HBr ]
k
[ Br2 ]

Where K = (
and K’ =
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 Cont…
Acid -baseCatalysis

38
Cont…

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 Cont…
Enzyme Catalysis
• Enzymes are proteins that act as catalysts in
biochemical
• Enzyme has active site where reactant molecule fits
reactions.

• A simple theory for the mechanism of enzymes was

proposed by Michaelis and Menten
• An Enzyme (E) converts a reactant (S) into products, (P).

First, the enzyme and substrate rapidly (k 1 and k-1 are large) form a complex, ES.
The decomposition of ES to form products is slow. We will ignore the backward reaction because
k-2 is small and P is small.
40
Cont…

41
Cont…

42
 Theories of reaction rate
There are two basic theories: Collision theory and activated complex theory
(transition state theory).
1. Collision theory
I. The basic requirement for a reaction to occur is that the reacting species must
collide with one another. This is the basis of collision theoryfor reactions.
II. The number of collisions that takes place per second per unit volume of the
reaction mixture is known as collision frequency(Z).
III. Every collision does not bring a chemical change. The collisions that
actually produce the product are effective collisions.
 The effective collisions, which bring chemical change, are few in
comparison to the total number of collisions.
 The collisions that do not form a product are ineffective elastic collisions,
i.e., molecules just collide and disperse in different directions with
different velocities. 43
 Cont…
Iv For a collision to be effective, the following two barriers are to be cleared,

 Energy barrier: “The minimum amount of energy which the colliding

molecules must possess as to make the chemical reaction to occur, is known as
threshold energy”.
 There is an energy barrier for each reaction. The reacting species must be
provided with sufficient energy to cross the energy barrier.
 Orientation barrier: The colliding molecules should also have proper orientation
so that the old bonds may break and new bonds are formed.
 For example,
 During this reaction, the products are formed only when the colliding
molecules have proper orientation at the time of collisions. These are called
effective collisions.

44
 Cont…

V Thus, the main points of collision theorya re as follows,

 For a reaction to occur, there must be collisions between the reacting species.
 Only a certain fraction of the total number of collisions is effective in forming the
products.
 For effective collisions, the molecules should possess sufficient energy as well
as orientation.
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 Cont…
Collision theory and reaction rate expression

46
 Cont…
 The activation energy (Ea) depends upon the nature of chemical bonds
undergoing rupture and is independent of enthalpies of reactants and products.
 According to the concept of activation energy, the reactants do not change
directly into the products.
 The reactant first absorb energy equal to activation energy and form
activated complex. At this state, the molecules must have energy at least
equal to the threshold energy.
 This means that the reaction involves some energy barrier which must be
overcome before products are formed.
 The energy barrier is known as activation energy barrier.

47
 Cont…
2. Transition state theory

 According to transition state theory the activated complex is supposed to be

in equilibrium with the reactant molecules.
 Once the transition state is formed it can either return to the initial reactants or
proceeds to form the products.
 Assuming that once formed the transition state proceeds to products we can
say that rate is proportional to concentration of transition state.
 Mathematically, Rate Transition state
 Rate= Constant × Transition state
 The activation energy for the forward reaction, (Efa and the activation energy
for the reverse reaction (Efa) are related to the enthalpy ( ) of the reaction
by the equation

48
 Cont…
Arrhenius equation
Arrhenius proposed a quantitative relationship between rate constant and
temperature as,
The equation is called Arrhenius equation.

49
Cont…

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