Fundamentals

of
reaction kinetics
OVERVIEW
 In many combustion processes, chemical
reaction rates control the rate of combustion,

 In essentially all combustion processes,

chemical rates determine pollutant formation and
destruction.

 The study of the elementary reactions and

their rates, chemical kinetics, is a specialized
field of physical chemistry
Global Versus Elementary Reactions
The overall reaction of a mole of fuel with a moles of
an oxidizer to form b moles of combustion products
can be expressed by the global reaction mechanism
Global Versus Elementary Reactions
(cont.)
 Elementary reactions occur due to collisions
between specific molecules in the gas phase

 Global reactions may be viewed as a result of

many of these elementary processes.

 From a rigorous point of view, a reaction rate may

only be attributed to elementary reactions.
.
Global Versus Elementary Reactions (cont.)
 The assumption of a single rate for a one-step
global reaction, which is very often used to describe
the structure of ignition and flame phenomena , can
therefore not be justified on the basis of chemical
kinetics.

 It, nevertheless, represents a useful ad-hoc

approximation in order to simplify the
mathematical analysis.
Global Versus Elementary Reactions (Cont’d)
From experimental measurements, the rate at
which the fuel is consumed can be expressed
as:

Where the notation [Xi] is used to denote the molar

concentration (kmol/s in SI units) of the ith
species in the mixture
GLOBAL VERSUS ELEMENTARY REACTIONS
(cont.)

 The constant of proportionality, is called the

global rate coefficient, and, in general, is
not constant, but rather is a strong function of
temperature.

 The minus sign indicates that the fuel

concentration decreases with time.

 The exponent n and m relate to the

reaction order.
 Global Versus Elementary Reactions (Cont.)
 The equation says that the reaction is nth order
with respect to the fuel, mth order with respect to
the oxidizer, and (n+m)th order overall

 For global reactions, n and m are not necessarily

integers and arise from curve fitting
experimental data.

 The use of global reactions to express the

chemistry in a specific problem is frequently a "black
box" approach.
Global Versus Elementary Reactions (Cont’d)

Although this approach may be useful in solving

some problems, it does not provide a basis

for understanding what is actually happening

chemically in a system.
Global Versus Elementary Reactions (Cont’d)

In reality, many sequential processes can occur

involving many intermediate species.

For example, consider the global reaction .

Global Versus Elementary Reactions (Cont’d)
To effect this global conversion of hydrogen and
oxygen to water, the following Elementary
reactions, are important:

• Among others
Global Versus Elementary Reactions (Cont’d)

• To have a complete picture of the combustion of

and , more than 20 elementary reactions can be

considered.
Global Versus Elementary Reactions (Cont’d)

-The elementary (one step) reaction may

be:
1- unimolecular

2- bimolecular

3- trimolecular
Bimolecular Reactions and Collision Theory
• Most elementary reactions of interest in
combustion are bimolecular; that is, two
molecules collide and react to form two different
molecules.

• For an arbitrary bimolecular reaction, this is

expressed as
•
Bimolecular Reactions and Collision
Theory (Cont.)

• The rate at which the reaction proceeds is

directly proportional to the concentrations of

the two reactant species, i.e.,

Bimolecular Reactions and Collision
Theory (Cont.))
• All elementary bimolecular reactions are overall
second order, being first order with respect to
each of the reacting species.

• The rate coefficient, again is a function of

temperature, but unlike the global rate
coefficient, this rate coefficient has a theoretical
basis.
Bimolecular Reactions and Collision
Theory (Cont.)
• If the temperature range of interest is not too great,
the bimolecular rate coefficient can be expressed
by the empirical Arrhenius form,

• Where A is a constant termed the pre-

exponential factor or the frequency factor.
Unimolecular Elementary Reactions
• As the name suggests, unimolecular reactions
involve a single species undergoing a
rearrangement (isomerization or decomposition)
to form one or two product species), i.e.,

or •
Other Elementary Reactions (Cont.)

• Examples of unimolecular reactions include

the typical dissociation reactions important to
combustion:

• e.g.,
Other Elementary Reactions (Cont.)

• Unimolecular reactions are first order at high

pressures:

while at low pressures, the reaction rate also depends

on the concentration of any molecules, M, with
which the reacting species may collide.
Other Elementary Reactions (Cont.)
In this case,

To explain this interesting behavior requires postulating

a three-step mechanism. Since we have yet to
explore some of the concepts required to deal
with this, we conclude our treatment of
unimolecular reactions for the time being.
Other Elementary Reactions (Cont.)

Termolecular reactions involve three reacting

species and correspond to the reverse of the
unimolecular reaction at low pressures.

The general form of a termolecular reaction is

Other Elementary Reactions (Cont.)
Recombination reactions such as

and

Are important examples of termolecular reactions

in combustion.

Termolecular reactions are third order, and their

rates can be expressed as
Other Elementary Reactions (Cont’d)
where, again, M may be any molecule and is
frequently referred to as a third body.

When A and B are the same species, as in

H + H + M,

a factor of two must multiply the right-

hand-side of equation since two A molecules
disappear to form C.
Reaction Rate
Law of mass action

The rate of a chemical reaction is proportional to the

concentration of reacting species.

For the reaction

a A +b B. ----- lL+mM
The rate of reaction will be :-

-d [A]/d t = -(a/b)*(d [B]/d t)

= (a /l)*(d[L]/d t) =(a /m )*(d [M]/d t)

-
Net Production Rates
 In the previous sections, we introduced
the idea of a sequence of elementary reactions
that leads from reactants to products, which
we termed the reaction mechanism.

 Knowing how to express the rates of elementary
reactions, we can now mathematically express
the net rates of production or destruction for any
species participating in a series of elementary
steps.
Net Production Rates (cont’d)

• For example, let us return to the H2-O2

reaction mechanism, which is incompletely
given by the previous 4 equations and
include both forward and reverse reactions

as indicated by the symbol:

Net Production Rates (cont’d)
Net Production Rates (cont’d)
• where,

are the elementary forward and

reverse rate coefficients,
respectively, for the ith reaction.
Net Production Rates (cont’d)

• The net rate of production of O2, for example,

is the sum of all of the individual
elementary rates producing O2 minus the
sum of all of the rates destroying O2 ; i.e.,
Net Production Rates (cont’d)
Net Production Rates (cont’d)

And for H atoms, •

Net Production Rates (cont’d)
• We can write similar expressions for each species
participating in the mechanism, which yields a system of
first-order ordinary differential equations that describes the
evolution of the chemical system starting from given initial
conditions, i.e.,
Net Production Rates (Cont.)
This set of equations couples with any
necessary statements of conservation of mass,
momentum, or energy, and state equations,
which can be integrated numerically using a
computer.

• Packaged routines, efficiently integrate the stiff

system of equations that arise in chemical
systems.
Net Production Rates (CONT’D)

• A set of equations is considered stiff when one or

more variables change very rapidly, while others
change very slowly.

• This disparity in time scales is common in

chemical systems where radical reactions are
very fast compared with reactions involving stable
species.
Reaction order:
For an overall reaction

May be zero or fraction or 1 , 2 , 3

If d c /d t= k c n

n is the reaction order

Reaction order (cont.):

Zero order reaction:

Rate equation takes the form

-d c /d t = k c 0 = k

Ct = C 0 + k t

eg 2N2O =2N2+O2
First order reaction :

Rate equation :
-d [A] /d t = k [ A ]

[A]= [A]0 e –k t

Eg.
O2 = 2O
 Ln
[A]/
Ln
[A]O
Ln
[A]O/ 2

-tanθ= K
θ
t 1/2 T

Representation of 1st order reaction

Second order reaction:
a A + b B = products

Type 1 : -d [A] /d t= k [A]2

Type 2 : -d [A]/d t = k [A][B]

“for type 1”
1/[A]= 1/[A0]+Kt
Eg.
2NO2 = 2NO+O2
1/[A]

2/[A]O

1/[A]
O

t 1/2 T
Representation of second order reaction
[ Type Ӏ ]
Third order reaction
a A +b B + c C = products

Type 1 : -d [A]/d t=k[A]3

Type 2 : -d [A]/d t=k [A]2 [B]

Type 3 : -d [A]/d t=k [A] [B] [C]

“for type 1” 1/[A]2 = 1/[A0]2+2Kt

The ‘n’ order reaction

-d [A]/d t=k [A] n

So
1/[A]n-1 = (n-1) k t
How to determine reaction order

-experimental
-measured concentration at different times are
plotted as :

L n c , 1/c ,1/c2, .... , 1/cn

The function giving a straight line gives the

reaction order
Half life: t1/2
-The time required to reduce the concentration of a
species to half its value

Reaction order t 1/2

1-Zero order [A0]/2K

2-First order ln2/k

3-Second order “type 1” 1/k [A0]

4-Third order “type 1” 3/2k [A0]2

5-nth order “type 1” 2n-1-1 /k[A0] n-1(n-1)

The Arrhenius equation:-
Experimental formulation of effect of temperature on
rates was suggested by Arrhenius to take the
form
K= A e-E/RT

A & E are empirical constant

This formula can be derived as follows :
For the reaction:-
A+B = C+D
The Arrhenius equation (cont.):
K f [A][B] =K b [C][D]

K p = [C][D]/[A][B] = K f/ K b

Ln K p = - d G /R T = -(dH - T d S)/ RT

d /d T Ln Kp= d /d T (d H/RT + d S/R)

= d H / R T2

Then d Ln Kp/d T = d H/RT2

Where d H is the heat of reaction : d H =E –E = E f-E b

The Arrhenius equation (con.):

As K p =K f/Kb
Then :

d (Ln K p)/ d T=d (Ln K f) /d T – d (Ln Kb)/d T = d H/ RT2

Then :

d (Ln K f)/ d T– d (Ln K b )/d T = E f –E b /RT2

Arrhenius suggested to separate the above equation into

two equation:
The Arrhenius equation (cont.):
d (Ln K f )/d T = Ef/RT2 Ln k

and d (Ln K b) /d T= Eb/RT2

or in general:

d Ln K / d T =E/RT2
1/T
Integrating:

Ln K = - E/RT +A
K = A e –E/RT
Activation energy :- E

Reaction system at equilibrium means that there is

an equilibrium between normal and active
species

Only active species take part in the chemical

reaction (Arrhenius)
Activation energy (cont.) :
The minimum energy a molecule possesses to be active is
called “activation energy”

This explains the marked influence of temperature on the

reaction rate.

An overall reaction may be looked upon as taking place by

the following two steps:

Reactants ---- active reactants ----- products

The energy change for the formation of active species is E f
and for the second part E b
Relation between Coefficient and Equilibrium
Constants
 Measuring rate coefficients of elementary reactions is a
difficult task that frequently leads to results that possess a
rather large degree of uncertainty.

 On the other hand, equilibrium constant, which are based on

thermodynamic measurements or calculations, are very
accurate and precise in most cases

 We can take advantage of accurate thermodynamic data in

solving chemical kinetics problems by recognizing that, at
equilibrium, the forward and reverse reaction rate must be
equal.
Relation between Coefficient and
Equilibrium Constants (Cont.)

• For example, consider both the forward and

reverse rates for the arbitrary bimolecular
reaction

• For species A, we can write

Relation between Coefficient and
Equilibrium Constants (Cont.)

• For the equilibrium condition,

• Which, upon rearranging, becomes

Relation between Coefficient and
Equilibrium Constants (Cont.)

• we defined before the equilibrium constant based

on partial pressures for an arbitrary equilibrium
reaction to be
 Relation between Coefficient and
Equilibrium Constants (Cont.)
• Where the superscripts are the stoichiometric
coefficients, i.e.,

• and

• Since the molar concentrations relate to the mole

fractions and partial pressures as follows ,
 Relation between Coefficient and
Equilibrium Constants (Cont.)
• We can define an equilibrium constant based on
molar concentrations, Kc. The relationship between
Kc and Kp is

• Or
 Relation between Coefficient and
Equilibrium Constants (Cont.)

• Where
Relation between Coefficient and
Equilibrium Constants (Cont.)

• From the above, we see that the ratio of forward and

reverse rate coefficients equals the equilibrium
constant Kc ,
Relation between Coefficient and
Equilibrium Constants (Cont.)

• Using the previous equation, one can compute

a reverse reaction rate from a knowledge of the
forward rate and the equilibrium constant for the
reaction; or, conversely, one can calculate the

forward rate knowing the reverse rate .

Relation between Coefficient and
Equilibrium Constants (Cont.)

• In performing kinetic calculations, the most

accurate experimental rate coefficient over the
temperature range of interest should be used, and
the rate in the opposite direction calculated from
the equilibrium constant.
Relation between Coefficient and
Equilibrium Constants (Cont.)

• The National Institute of Standard and Technology

(formerly the U.S. Bureau of Standards)
maintains a chemical kinetics database
providing rate information on well over 6000
reactions .
 Steady-State Approximation
• In many chemical systems of interest to combustion, highly
reactive intermediate species, e.g., radicals, are formed.

• Analyses of such systems can sometimes be simplified by

applying the steady-state approximation to these reactive
intermediates or radicals.

• Physically, its rate of formation and its rate of destruction are

equal
Steady-State Approximation (Cont.)

 This situation typically occurs when the reaction

forming the intermediate is very slow, while the
reaction destroying the intermediate is very fast.

 As a result, the concentrations of the radical are

quite small in comparison with those of the
reactants and products.
 Steady-State Approximation (Cont’d)

A good example of this is the Zeldovich

mechanism for the formation of nitric oxide,
where the reactive intermediate of interest is the
N atom:
 Steady-State Approximation (Cont’d)

• The first reaction in this pair is slow and, hence, rate

limiting; while the second is extremely fast.
• We can write the net production rate of N atoms as
Steady-State Approximation (Cont.)
• After a rapid transient allowing the buildup of N atoms to
some low concentration, the two terms on the right-hand-
side of Eqn.4.44 become equal, and d [N]/dt approaches
zero. With d [N]/dt 0,

• we are able to determine the steady concentration of N

atoms:
Steady-State Approximation (Cont.)

• Although invoking the steady-state

approximation suggests that does not
change with time, may change as it
rapidly readjusts according to equation 4.46
 Any Questions ??
.
Prof. Dr. Mahmoud Elkady