Jishnu Bhattacharya

1st Semester - 2016-17

Lecture -6

Chemical Kinetics
In a real-life combustion system (such as IC engine or boiler), several
chemical reactions happen simultaneously some are slow and some are
fast. The following questions arise naturally:
What is the final equilibrium composition with known initital
state?
How fast a chemical reaction attains its equilibrium state?
What are the mechanisms by which the chemical reactions
proceed?

Chemical Kinetics
We have learnt how to find the equilibrium composition (at least for
a single combustion reaction). However we do not know how much
minimum time we should allow to reach this state.
The reaction mechanisms dictate the phenomena like Ignition,
flame propagation, flame extinction etc.
The pollutant formation or destruction during a combustion process
is closely related to the kinetics of the reaction.

Basic reaction kinetics

Rate of a reaction depends on the condition. The basic conditions are:
Temperature
Pressure
Concentrations of the reactants
A general reaction can be written as:

i =1

i =1

'
''
v
M

v
i i i Mi

N: total number of species in reactants and products

M: a species

vi' : Number of moles of species Mi in reactants

vi'' : Number of moles of species Mi in products

Basic reaction kinetics

N

''
v
M

v
i i Mi
i =1

For example:

'
i

i =1

3CH 4 + 7O2 + 4 N 2 CO2 + 2CO + 6 H 2O + O2 + 4 N 2

Here, N = 6 : CH4, O2, N2, CO2, CO, H2O

M1= CH4

M2= O2

M3= N2

M4= CO2

M5= CO

M6= H2O

V1 = 3

V2 = 7

V3 = 4

V4 = 0

V5 = o

V6 = 0

V1 = o

V2 = 1

V3 = 4

V4 = 1

V5 = 2

V6 = 6

Elementary Reaction
A reaction seldom happens as the last example
Rather, it happens through collision of molecules and destruction of
existing bonds followed by creation of new bonds
A overall (global) reaction consists of several of such reactions
which are called Elementary Reactions.
Intuitively, the elementary reactions are mostly unimolecular
(where one molecule dissociate to form more-than-one species) or
bimolecular (where two molecules collide to form some other species)
Note: There are examples of trimolecular elementary reactions as well; however,
they are rare and we exclude them from the scope of this introductory course.

Elementary Reaction
Example of an elementary reaction:

H + O OH

A general elementary reaction can be written as:

aA + bB cC + dD
Now rate of this reaction (RR) can be expressed as the rate of
formation of products or rate of destruction of reactants:

RR =

1 dC A
1 dC B 1 dCC 1 dC D
=
=
=
a dt
b dt
c dt
d dt

The normalization by the stoichiometric coefficient is necessary as

the rate of reaction is independent of the choice of species for
concentration-evaluation.

Elementary Reaction
As rate of an elementary reaction will depend on the number of
collisions between the relevant molecules, we can expect that the rate
will be proportional to the concentrations of the reactant molecules.
If we consider the last example,

H + O OH

RR C H CO
For the general reaction

aA + bB cC + dD ,

RR C Aa C Bb

Law of Mass Action

RR C C
a
A

b
B

This is known as the Law of Mass Action and it states that

The rate of an elementary reaction is proportional to the concentrations of
the participating chemical species (i.e., reactants) raised to the power of their
individual stoichiometric concentrations.
In general form,

RR

vi
C
Mi

M i Re ac tan ts

OR

RR = k

vi
C
Mi

M i Re ac tan ts

k = proportionality constant known as rate coefficient or specific reaction

rate

Law of Mass Action

RR = k

vi
Mi
M i Re ac tan ts

Only valid for elementary reactions

For a global reaction, the rate of reaction have to found out on the basis of
the rate of reactions of the elementary reactions.
How to find the rate coefficient (k)?

Law of Mass Action

RR = k

vi
Mi
M i Re ac tan ts

Only valid for elementary reactions

For a global reaction, the rate of reaction have to found out on the basis of
the rate of reactions of the elementary reactions.
How to find the rate coefficient (k)?

Collision theory

Collision Theory
A chemical reaction occurs only when
Suitable molecules collide
Collision occurs in suitable orientation
Colliding molecules possess energy greater than a threshold energy
(called activation barrier)
Quantitatively, rate of reaction is expressed as

RR = Z AB S exp( E / RT )
Collision
Frequency

Steric (orientation)
Factor

Probability of having an
energy E @ temperature T

Collision Theory
By obtaining expressions for the collision frequency and steric factor form
the kinetic theory of gases, one can obtain RR in the following form.

RR = BT 0.5C Aa C Bb exp( E / RT )
A Constant
Comparing with the law of mass action

RR = kC Aa C Bb

, we get

k = BT 0.5 exp( E / RT ) = A exp( E / RT )

Rate Coefficient

Kinetic preexponential factor

Rate coefficient
A

ln k

slope = E / R

1/ T

From experimental
observations, both A and E
can be found out from this
plot.

Rate coefficient
A

ln k

slope = E / R

1/ T

From experimental
observations, both A and E
can be found out from this
plot.

Note:
In nature, there are many quantities which
follow this kind of exponential rule In
general, this is called Arrhenius rule.

Rate coefficient
We know that the pre-exponential factor (A) is a weak function of temperature

k = BT 0.5 exp( E / RT ) = A exp( E / RT )

We can incorporate the variation of A with temperature by plotting the same
curve in different temperature zones

Rate coefficient
High temperature
Low temperature

ln k

1/ T