CH1001: CHEMISTRY

CHEMICAL KINETICS

Dr. Venkateswara Rao Mundlapati

Chemistry Department, School of Applied Sciences
KIIT University, BBSR
venkateswara.mundlapatifch@kiit.ac.in
Rate of Reaction
Chemical Kinetics
Rate of Reaction
Rate of Reaction
Rate of Reaction
Rate of Reaction
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 Problems
Q1. In the reduction of nitric oxide, 50% of reaction was completed in 108 sec
when initial pressure was 336 mm Hg and in 147 sec initial pressure was 288 mm
Hg. Find the order of the reaction.
2NO + 2H 2 → N 2 + 2H2O

Q2. In the thermal decomposition of a gaseous substance, the time taken for the
decomposition of half of the reactant was 105 min when the the initial pressure was
750 mm and 950 min when the initial pressure was 250mm. Find the order of the
reaction.
Q3. The half-life for the thermal decompostion of phosphine at three different
pressures are given below: Find the order of the reaction.
P (mm Hg) 707 79 3.5
t0.5 84 84 84
Q4. For the reaction between gaseous chlorine and nitric oxide, it is found that
doubling the concentration of both reactants increases the rate eight times, but
doubling the chlorine concentrationalone doubles the rate. What is the order of
reaction with respect to nitric oxide and chlorine?
2NO + Cl2 = 2NOCl
 Problems
Q5. The half-life of a chemical reaction at a particular concentration is 50 min.
When the concentration is doubled, the half-life become 100 mins. Find out the
order of the reaction.
Q6. The half-life of a chemical reaction at a particular concentration is 50 min.
When the concentration is doubled, the half-life remains 50 mins. Find out the
order of the reaction.
Q7. The half-life of a chemical reaction at a particular concentration is 50 min.
When the concentration is doubled, the half-life become 25 mins. Find out the
order of the reaction.
Q8. Compound A decomposes to form B and C is a first order reaction . At 25 C
the rate constant for the reaction is 0.45 s -1 . What is the half-life of A at this
temperature.
Q9. The half-life of a susbstance in a first order reaction is15 minutes. Calculate
the rate constant.
Q10. For a certain first order reaction, half-life is 100 sec. How long will it take for
the reaction to be completed 75% ?
Q11. 50% of a first order reaction is completed in 23 min. Calculate the time
required to complete 90% of the reaction.
 The Steady-State Approximation

R Int P

When a reaction involves one or more intermediates, the concentration of one of the
intermediates remains constant at some stage of the reaction. Thus, the system has reached a
steady-state. The concentration of one of the intermediates, [Int], varies with time as shown
in Figure

Rate of Rate of
formation of = disappearance
intermediate of intermediate

= - time
 Complex Reactions
Type - II

Intermediate is formed in the first fast equilibrium step which

subsequently slowly reacts in the second rate determining step.
 Complex Reactions
Type - II
Mechanism of the reaction is

As the product NOCI is being formed in second step, so we can

consider the rate of formation of product as the overall rate of
the reaction.

-------Eqn.(1)
 Complex Reactions
Type - II
For the calculation of concentration of intermediate, [NOCl2], we
can apply the steady state approximation.
Rate of formation of Intermediate, NOCI2 = Rate of consumption
of intermediate, NOCl2

-------Eqn.(2)
 Complex Reactions
Type - II
Substituting the value of [NOCl 2 ] from equation (2) into
equation (1), we get

-------Eqn.(3)
 Complex Reactions
Type - II
Assuming k2 [NO] << k-1 and neglecting the former, we get

The overall rate of the reaction

 Complex Reactions
Type - III

k
2

Such reactions involve more than two elementary steps with

atleast one slow step
 Complex Reactions
Type - III
The reaction for the formation of phosgene

For this reaction, the following mechanism has been

proposed :

k2

k-2
 Complex Reactions
Type - III
From step (iii), the rate of formation of phosgene is

-------Eqn.(1)

From step (ii)

- ------Eqn.(2)

From step (i)

-------Eqn.(3)
 Complex Reactions
Type - III
Substituting the value of [Cl] from equation (3) in equation
(2), we get

-------Eqn.(4)

Substituting this value of [COCl] from equation (4) in equation

(1), we get
 Complex Reactions
Type - III
 Complex Reactions
Type - IV

Complex reactions with more than one step having comparable

rate constants (i.e., it is not known whether the steps are slow
or fast).
 Complex Reactions
Type - IV
The decomposition reaction of gaseous nitrogen pentaoxide

The following mechanism has been proposed

k3
 Complex Reactions
Type - IV
From step (ii) we have

-------Eqn.(1)

Applying the steady-state approximation principles to

intermediates NO and NO3 we get

k3

-------Eqn.(2)
 Complex Reactions
Type - IV

-------Eqn.(3)

Substituting [NO] from equation (2) in equation (3), we get

-------Eqn.(4)

Substituting [NO3 ] from equation (4) in equation (1), we get

 Complex Reactions
Type - IV
 Theories of Reaction Rates

Collision Theory

Absolute Reaction Rate Theory

Or
(Transition State Theory)
 Collision Theory

According to this theory, a chemical reaction takes place only by

collisions between the reacting molecules.

➢ The molecules must collide with sufficient kinetic energy.

Energy barrier

Ea = Activation Energy
 Collision Theory

➢ The molecules must collide with correct orientation.

Thus, only molecules colloid with kinetic energy

greater than activation energy and with correct
orientation can cause reaction.
Collision Theory & Reaction Rates:

A + B Product

Rate = f  p  z
Where, f = fraction molecules having sufficient kinetic energy
p = probable fraction of molecules with effective orientation
z = collision frequency
The Collision Theory of Chemical Reactions
This theory is satisfactory for gaseous reactions. The essential
requirements for reactions according to collision theory are :

1. Collisions between the reactant molecules.

2. Activation of molecules.
3. Proper orientation at the time of collision.
Consider a reaction between two reactants R1 and R2
Rate of collisions= Constant x [ R1 ] [ R2 ]

It is assumed in collision
theory that a collision is
successful only if the
molecules collide with at
least the activation energy of
the reaction
The Collision Theory of Chemical Reactions
Therefore the activation energy is the minimum energy
required for reaction. The fraction of collisions with at least the
energy Ea is given by the Maxwell distribution of speeds
The Collision Theory of Chemical Reactions
Interpretation of the graph:
At low temperature only a very tiny fraction of molecules have
enough energy to react. At higher temperature, a much larger
fraction of molecules can react.

Consider the reaction

The Cl atom reacts with the HI

molecule only if its line of approach
is inside a cone of half-angle 30°
surrounding the hydrogen atom
The Collision Theory of Chemical Reactions
Let us now find rate expression for a bimolecular gaseous
reaction
-------Eqn.(1)
According to collision theory

-------Eqn.(2)

where:
Z11 is the number of collisions between the reacting molecules
per second per dm3
θ is the fraction of the total number of molecules which are
activated, and

p is referred to as the probability or stearic factor and is related

to the geometry of the molecule.
Kinetic theory of gases
The Collision Theory of Chemical Reactions
From the kinetic theory of gases

-------Eqn.(3)

-------Eqn.(4)

-------Eqn.(4a)
The Collision Theory of Chemical Reactions

-------Eqn.(5)

Therefore from Eqn. 3, 4 and 5 we have

-------Eqn.(6)

Limitations
(i) This theory is applicable to gaseous molecules,
(ii) It is difficult to calculate p, the stearic factor from molecular
geometry for complex molecules.
Transition State Theory of Reaction Rates
or Absolute reaction rate
 Transition State Theory of Reaction Rates
All the reactions proceed through an activated or transition
state which has energy higher than the reactants or products. It
is assumed that an equilibrium is established between the
reactants and the activated complex.

-------Eqn.(1)
The rate of such a reaction depends on :
(i) concentration of the activated complex molecule
(ii) the rate at which it decomposes.

As the activated complex is in equilibrium with the reactants

 Transition State Theory of Reaction Rates

-------Eqn.(2)
As the activated complex [ R1 R2] # is unstable so at a
particular vibration it decomposes to form products. The
rate of decomposition of the complex is dependent (proportional)
to the frequency of vibration.

-------Eqn.(3)

According to Planck's expression

-------Eqn.(4)
The average energy of such a vibrational degree of freedom is
given by kT, where k is Boltzmann's constant. Therefore we have
Transition State Theory of Reaction Rates

-------Eqn.(5)

-------Eqn.(6)
Transition State Theory of Reaction Rates

-------Eqn.(7)

-------Eqn.(8)
 Transition State Theory of Reaction Rates
Now taking logarithm of equation (6), we get

Differentiating w.r.t. temperature, we obtain

-------Eqn.(9)

As the variation of equilibrium constant with temperature is given

by

-------Eqn.(10)
 Transition State Theory of Reaction Rates
From equations (9) and (10), we get

-------Eqn.(11)

-------Eqn.(12)
 Transition State Theory of Reaction Rates
For ideal gases

-------Eqn.(13)

Substituting the value of ∆E# from equation (13) in equation

(12), we get
-------Eqn.(14)
 Lindemann Unimolecular Reactions
An elementary reaction is unimolecular if the rearrangement of
a single molecule or ion produces one or more molecules of
product.

In unimolecular reactions, only one reactant molecule takes

part in the reaction like
-------Eqn.(1)
According to this theory, the reactant molecules (R) are first
activated by collisions with other reactant molecules.
 Lindemann Unimolecular Reactions

The activated reactant molecule do not decompose immediately

but it remains in the activated state for a finite time. There is a
time lag before decomposition of the activated reactant
molecules. During this time lag, the activated molecules may
get deactivated to ordinary molecules in second biomolecular
collisions.

If in the time lag, activated reactant molecules are not

deactivated, they will undergo a decomposition reaction
leading to the formation of products.
 Lindemann Unimolecular Reactions
In this mechanism, according to Lindemann, the activated
reactant molecules are produced as reactive intermediate. So,
we can apply steady-state-approximation to find out the
concentration of this short-lived species.
 Lindemann Unimolecular Reactions
As the products are being formed in the last step.
 Effect of Temperature on Reaction Rates
Temperature dependence of reaction rates can be studied by
plotting a graph between rate constant (k) and temperature
(I) for different reactions as shown below

This curve is applicable for most

of the reactions and indicates
that rate increases with increase
in temperature. This is easy to
understand because number of
effective collisions between the
reactant molecules increases
with increase in temperature.
Thus, rate increases.
 Effect of Temperature on Reaction Rates

This curve is applicable for enzyme catalyzed reactions because

enzy m es show maxim um e f f i c i e n c y at some optimum
temperature, beyond which they undergo denaturation.
 Effect of Temperature on Reaction Rates
The ratio of the rate constants of a reaction at two temperatures
differing by 10° C is known as temperature coefficient of the
reaction.

A more correct dependence of k on temperature is given by

Arrhenius equation

-------Eqn.(1)
 Effect of Temperature on Reaction Rates
In equation (1), e -Ea/RT represents the fraction of molecules
having energies equal to or greater than the energy of activation.
Taking logarithm of equation (1),

-------Eqn.(2)
 Effect of Temperature on Reaction Rates

Thus, a plot of log k versus 1/T should be a straight line (above

figure) with slope equal to - Ea /2.303 R and intercept equal to
log A so from the slope of this plot the activation energy can be
evaluated.
 Effect of Temperature on Reaction Rates

From equation (2), we get

-------Eqn.(3)

-------Eqn.(4)

From equations (4) and (5),

Effect of Temperature on Reaction Rates

-------Eqn.(5)
 Effect of Temperature on Reaction Rates
A first order reaction has rate constant of 4500 s-1 at 1 °C and an
activation energy of 58000 J.mol-1 At what temperature would
rate constant be 10,000 s-1 ?
 Effect of Temperature on Reaction Rates
For the reaction

The following data was obtained :

The rate constant at 500 °C was 5 x 103 s-1, find rate constant at
600 °C. Given Ea = 50,000 J mol-1
Solution