CHEMICAL KINETICS

(Part- I)
1. Introduction

2. Complex reaction and its rate expression: Steady state

Approximation

3. Rate laws for opposing, parallel and consecutive reactions

4. Theories of reaction rate:

(i) Collision theory
(ii) Lindeman’s time lag theory for unimolecular reactions
(iv) Transition state theory or absolute reaction rate theory
 Introduction

Chemical kinetics is the branch of physical chemistry that is concerned with

understanding the rates of chemical reactions.

A chemical reaction is, by definition, one in which chemical substances are

transformed into other substances, which means that chemical bonds
are broken and formed with changes in the relative positions of
atoms in molecules. At the same time, there are shifts in the arrangements
of the electrons that form the chemical bonds. A description of a reaction
mechanism must therefore deal with the movements and speeds of atoms
and electrons. The detailed mechanism by which a chemical process
occurs is referred to as the reaction pathway.

A reaction may be single step or multistep.

Kinetic measurements provide evidence for the mechanism of the
individual elementary steps.
Reaction rate can be measured in terms of change of concentration of
the reactants or products over the time.

For the following reaction:

aA + bB cC+ dD
Here a, b, c, d are the corresponding
stoichiometric coefficients.
reactants products

- d[A] - d[B]
Rate of disappearance of reactant = =
dt dt

d[C] d[D]
Rate of formation of product = =
dt dt
1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate of reaction = - =- = =
a dt b dt c dt d dt
Rate of a reaction can be expressed in terms of rate law which relates rate of
a reaction with concentration of reactants and rate constant (k).

with respect to
reactants only

Small k Large k
 A recapitulation of the concepts of order, molecularity and
rate expressions

experimentally
determined

theoretically
understood
For elementary (one step) reaction, order = molecularity
Rate laws, graphical plots and half lives for zero, 1st and
2nd order reactions:

Continued..
3.

Considering each step

as first order, reactant
conc. falls over time and
product conc. rises with time
exponentially and intermediate
conc. starts from zero, reaches
maxima and again falls back
to zero

A P

concentration
I

time
 2NO + Cl2 2NOCl
k1
Step 1: NO + Cl2 NOCl2
k-1

k2
Step 2: NO + NOCl2 2NOCl

Show that overall rate of reaction is k[NO]2[Cl2]

where k = k1k2 / k-1 (assume that k2[NO] << k-1)

Comment on overall order of the reaction.

For the reaction H2(g) + I2(g) 2HI(g)

following mechanisms have been proposed-

k1
I2 2I fast
k-1
k2
H2 + 2I 2HI slow

Show that
½ d/dt[HI] = k1k2/k -1 [H2][I2]
FACTORS AFFECTING THE RATE OF REACTION
 TEMPERATURE
Rate of reaction is generally increased by increasing the temperature of the
reaction.
If we increase the temperature of a reaction by 10 °C, then rate of the reaction is
Increased approximately 2-3 times. This is called temperature coefficient.

MAXWELL--BOLTZMANN DISTRIBUTION
MAXWELL
 COLLISION THEORY
Hard sphere collision theory derives an expression for the rate law of a
bimolecular elementary gas phase reactions.

Assumptions:

(i) Molecules are considered to be hard rigid spheres.

(ii) For a reaction to occur between two molecules they must collide with each other (Z),
but not all collisions can produce reactions. Only effective collision can give the product.

a) Energy criteria: Energy of the molecule should be greater than the

threshold energy (f)
b) Properly orientated (P)

Rate of the reaction = Z f P

 Let us consider the following reaction: Reaction between same molecules

A+A Product

Number of binary collisions occurring per unit volume per unit time in the
reaction vessel is given by(Collision frequency, Z)

ZAA = 1/√2 .πσ2 v n2

Here σ is the closeness of approach between the two colliding A molecules or

diameter of A molecule, v is the average velocity of a gas molecule and n is
number of A molecules per unit volume in the reaction vessel
Rate of the reaction depends on (i) ZAA
(ii) and the fraction of molecules (f) for which relative translational kinetic
energy of the colliding molecules exceed threshold energy (e –Ea/RT)
Rate of the reaction = Z f P = 1/√2 .πσ2 v n2 e –Ea/RT P
= 2 σ2 n2 √(πRT/M) e –Ea/RT P
8RT
As v = √ πM
Rate of the reaction (R) ∞ √T
Rate of the reaction (R) ∞ e –Ea/RT
 FIND OUT WHICH TEMPERATURE FACTOR CONTROLS
THE RATE OF REACTION

Rate of the reaction (R) ∞ √T

Compare the rate at two different temperatures 300 K and 310 K

Rate of the reaction (R) ∞ e –Ea/RT

Compare the rate at two different temperatures 300 K and 310 K
 Activation Energy: Arrhenius Equation

Activation Energy (Ea): The potential energy barrier that must be surmounted
before reactants can be converted to products.
 The Arrhenius Equation

Fraction of molecules having

energy more than threshold
energy

Rate of a reaction is directly proportional to the temperature

The difference between the minimum

energy to bring out the molecular
rearrangement and the average energy of
the reactant molecules is known
as the activation energy of the reaction.
 Activation Energy: Calculation
Graphical method:

ln K = ln A –Ea/ RT
Log K = log A-Ea/2.303RT
 Activation Energy: Calculation
Analytical method:

Subtracting equation (ii) from equation (i) and applying logarithm in both sides,
we get
Activation Energy: Calculation
 Lindemann time lag theory of unimolecular reaction

Let us consider the reaction A B

The steps involved are as follows:

k1
A+M A* + M
K-1
k2
A* B (pdt.)
M may be solvent or an other
molecule present in the reaction
vessel

A time lag exists between energisation of A to A* and the

de-Composition of A* to product.
When the time lag is sufficiently large, A* can be de-
energized back to A and a near equilibrium is reached in
step 1
 Utilize it’s excess vibrational energy and undergoes
decomposition to form the product (B)

A* has two options

Deenergize back to the reactant A and gives back

the excess vibrational energy to kinetic energy of M

Kinetic aspects:
Rate of the reaction = d[product]/dt = k2 [A*] … (i)

d[A*]/dt = 0 using steady state approximation

k1[A][M]
Expanding, k1[A][M]-k-1[A*][M]-k2[A*] = 0 or [A*] = … (ii)
K-1[M]+k2
 Substituting [A*] from equation (i) in equation (ii) we get,
k1[A][M]
Rate of the reaction = k2 .
K-1[M]+k2
High pressure
Case 1: When k-1>>k2 zone
k1[A][M]
Rate of the reaction = k2 . = k1k2/k-1 [A]
K-1[M]

Hence rate of the reaction is 1st order with respect to A

Case 2: When k2 >> k-1
Rate of the reaction = k1[A][M]

Hence rate of the reaction is 2nd order

Low pressure
zone
 Transition state theory or absolute reaction rate theory

Transition state theory derives an expression for temperature dependence

of rate constant for the bimolecular reaction A +B Product

Assumptions:
(a) An activated complex [AB]‡ is formed from the two
reactant molecules.
(b) The complex exists at top of the potential energy
barrier and maintains a near equilibrium with the
reactants .
(c) The decomposition of the complex leads to formation [AB]‡
of products . ν
` A +B [AB]‡ Product
(d) Rate of the reaction depends on concentration of the
activated complex [AB]‡ and the frequency (ν) with
which the activated complex passes over the energy
barrier. A+B
Rate = [AB]‡ . ν = [AB]‡ kBT/h … (i)

Reaction coordinate
 Kc‡
` A +B [AB]‡ Product
Here K c ‡ is the equilibrium constant for the step of activation
[AB]‡
K c ‡= Or [AB]‡ = [A] [B] K c ‡ …(ii)
[A] [B]

Substituting [AB]‡ in equation (i) from equation (ii) we get,

Rate = [A] [B] K c ‡ kBT/ h … (iii)

k
Since the overall reaction is A+ B Product where k is the rate constant

rate law for this reaction is Rate = k [A][B] … (iv) from thermodynamic
point of view, where
ΔG ‡ is Gibb’s free
Comparing equations (iii) and (iv), k = K c ‡ kBT/ h
energy for activation
ΔH ‡ is enthalpy of
k = kBT/ h . e -ΔG / RT
‡
Hence activation and ΔS ‡ is
entropy of activation
k = kBT/ h . e -ΔH / RT . e ΔS / R
‡ ‡
Or
Activation energy Ea is related to enthalpy of transition by the following equation
Ea = ΔH‡ + RT - Δn ‡RT
Δn ‡ is the change in number of moles from product to reactants

For unimolecular reaction: Δn ‡ = 0, hence Ea = ΔH‡ + RT

k = kBT/ h . e -ΔH / RT . e ΔS / R
‡ ‡

hence k = kBT/ h e . e -Ea/ RT . e ΔS / R

‡

For bimolecular reaction: Δn ‡ = -1, hence Ea = ΔH‡ + 2RT

2
k = kBT/ h e . e -Ea/ RT. e ΔS / R
‡
hence
 Comparison between collision theory and transition state theory

1. Collision theory: Based on kinetic theory of gases and is valid for bimolecular
reactions
Transition state theory: Based on thermodynamics and is valid for both
bimolecular and unimolecular reactions.
2. Collision theory: The driving force is collision between the reactant molecules

Transition state theory: The driving force is loose vibrational degree of freedom
associated with the activated complex or transition state.

3. Collision theory: The temperature dependence of the rate constant expression is

k = A’ p √T e –Ea/RT
Transition state theory: The temperature dependence of the rate constant
expression is
k = kBT/ h . e -ΔH / RT . e ΔS / R
‡ ‡

Transition state theory considers orientation of the reactant molecules at the top of the
potential energy barrier with the inclusion of factor ΔS ‡ . ΔS ‡ negative means reactant
molecules are less ordered than the transition state and that is generally found in practice.
Hence this theory does not need any p factor in the rate equation like collision theory
Rate law for a parallel reaction

A D
 Continuing

d[A]
= - (k1+k2) [A]
dt
d[C]
[A] t Rate of formation of C =
d[A] dt
or
∫ [A]
=
∫
- (k1+k2) dt
= k1 [A]
[A]0 0

or ln [A]0 = (k +k )t d[D]
1 2
Rate of formation of D =
[A]
dt
= k2 [A]

Hence ratio of two rates is a constant k1 /k2

Rate law for a parallel reaction
 Rate law for an opposing reaction

Consider the following reaction

kf
Both forward and backward reactions follows of first
A B order kinetics
kb
At t=0, a 0

At t=t, [a-x] x
forward reaction backward reaction
Net rate of formation of B = Rate of disappearance of A – Rate of disappearance of B
or dx/dt = kf (a-x) – kbx … (i)

At equilibrium, the rates are equal, hence dx/dt = 0, hence

kf (a-xe) – kb xe = 0 when xe is the concentration of B at equilibrium

or kb = kf (a-xe) / xe … (ii) and kf + kb = kf a / xe … (iii)

 Substituting kb in equation (ii) from equation (i), we get

or dx/dt = kf (a-x) – {kf (a-xe) / xe } . x

kf > kb

concentration
x
or dx/dt = kf a (1 – )
xe

dx Kf a
or
∫ x -x
e
=
xe
∫ dt
kf = kb

concentration
or ln xe from (iii) Reactants
= (kf + kb) t
xe - x

Equilibrium
Products
Rate law for an opposing reaction
 Rate law for a consecutive reaction:
Example of consecutive reaction

Consider the following reaction

k1 k2
A B C

Assumptions:
(i) each step is first order and (ii) k2<<k1 which indicates 1st step is the r.d.s.

[A] = [A]0e-k1t … (i) where [A]0 is the initial concentration of A

Net rate of formation of B = d[B]/dt = k1[A] – k2[B] = k1 [A]0e-k1t – k2[B] (from (i))
or d[B]/dt + k2[B] = k1 [A]0e-k1t

solving 1st order differential

equation or [B] = k1 [A]0 (e-k1t – e-k2t) … (ii)
k2-k1
According to assumption (ii)

k1 [A]0 . e-k1t
[B]=
…(iii)
k2
Using steady state approximation, d[B]/dt = 0 if B is an intermediate

Hence, k1[A] – k2[B] = 0 equation (iii)

k1 [A]0 . e-k1t
or k1[A] = k2[B] and [B] =
k2

[C] = [A]0 – [A] – [B]

k1 e-k1t
Hence , [C] = [A]0 ( 1- e-k1t - ) from equation (ii) and (iii)
k2
Continuing

concentration
A C

Hence , [C] = [A]0 ( k2- k2e-k1t - k1e-k1t

) B

k2
time
k2- (k2 + k1 )e-k1t
or [C] = [A]0 { k2 }
or assumption (ii)
[C] = [A]0 (1 –e-k1t)

Product concentration
depends on rate constant
of slowest step.

Find out [C] when k1 > k2

 ln(k2/k1)
Show that B achieves max. concentration at time
(k2 – k1)

k1 [A]0 (e-k1t – e-k2t)

[B]=
k2-k1
-k1t -k2t
d[B]/dt = k1 [A]0 (-k1 e + k2 e ) =0
At t = tmax d[B]/dt = 0
k2-k1

ln(k2/k1)
or tmax =
(k2 – k1)