Chapter 2.

Reaction rate and Mechanism

Chemical reactions
 are processes in which reactants are transformed into products.
In single processes /Single rxn/, the change occurs directly and the
complete description of the mechanism of the reaction present can be
relatively obtained.
In multiple processes / Multiple rxn/, the reactants undergo a series
of step-like changes and each step constitutes a reaction in its own
right.
The overall mechanism is made up of contributions from all the
reactions that are sometimes too complex to determine from the
knowledge of the reactants and products alone.
Chemical kinetics
 is the study of the rate and mechanism in
the reactor
 is concerned about the quantities of the
reactants and the products, analyzing the
dynamics of chemical reactions, and their
rates of change.
Note that
Chemical kinetics does not provide
information on the energetic state of the
individual molecules.
Because a measured rate shows a statistical
average state of the molecules taking part in
the reaction.
2.1.The rate of chemical conversion

The rate of chemical conversion can be define in to two

ways
 The rate of production /formation
(Species – dependent rate)
 The rate of reaction (Species –
independent rate)
2.1.1. The rate of production /formation
 can be expressed using mole balance either
in the rate of disappearance of the reactants
or the rate of the formation of the products.

Consider a system in which one stoichiometrically

simple reaction taking place, a rate of production
can be define as:
Rate of formation of product
r  rate of formation of product " j" (moles " j" formed / time)
j unit(something)
 Rate of disappearance of reactant
 r  rate of disappearance of reactant " j" (moles " j" consumed / time)
j unit(something)

and it can be

 Since reactants disappear in reactions, their rate

expressions are given a negative sign.
 The amounts of the products increase and their rates
of change are therefore positive.
“Unit (something)”, we need to know where the reaction actually
takes place (system's geometry) . Hence the rate production
definition in equation is varying, based on the system reaction
(system's geometry) .
Let us consider a few most important cases
Batch process
is formally defined as the rate of change of mole of
one of the reactants or products per unit time and
per unit volume of the reaction mixture

r  moles j consumed or formed /time (2. 3)

j volumeof mixture

or in equation 1 dn j
rj  (2. 3.1)
V dt
 PFR dF j
rj 
dV

CSTR
F j,0 - F j
rj 
-V

Once again Remember !

The rate of production is defined as the time rate of
change in the quantity of a particular species (say A)
participating in a reaction divided by a factor that
characterizes the reacting system's geometry.
 Hence
Rate of production definition is varying, based on
factor that characterizes the reacting system's
geometry

a) Based on the unit volume of reacting fluid

dn
r  1 j  moles j formed /time
j V dt Volumeof fluid
f
b) Based on the unit mass of solid in fluid solid system

I dn
r j  1 j  moles j formed /time
M dt Massof solid
c) Based on the unit surface in two-fluid system or based on the
unit surface of solid in gas-solid system

II dn
r j  1 j  moles j formed /time
S dt Surface
d) Based on the unit volume of solid in gas-solid system

III dn
r j  1 j  moles j formed /time
V dt Volumeof solid
S
It can be seen that the above equations hold good, where the
form of the functional relationships of the rate change
represented by dn j remains the same
dt
Functional relationship b/n rates
dn
j V r Mr I  S r II V r III
dt f j j j s j
 volume of   mass of  I  surface of  II
 r j   r j   r j
 fluid   solid   solid 

 volume of  III
 rj
 solid 
 Consider the rate of formation as
1 dn j (2. 3.1)
rj 
V dt
The influence of volume changes in the reaction can be
observed taking equation (2. 3.1)
dC C
r  1 d (CjV )  j  j dV
j V dt dt V dt

•For constant volume becomes

dCj
rj 
dt
 •For variable volume becomes
dC C dV
rj  j
 j
dt V dt

Using Pressure to determine the rate

In gases the most used quantity is the rate of change of partial
pressure, and the rate of formation for batch reactor is defined
for perfect gas and constant volume

dn
1 j 1 dP (2. 3.2)
rj   j
V dt RT dt
Relationship between rate of production of
various species
Recalling equation for extent of reaction

n j  n j ,0


j

Differentiating gives us
dn j
d 
 (2.5)
j
 As per Stoichiometric law, i.e the change in number of moles are
directly related to the stoichiometric number, (Law of Definite
Proportions) thus

n A n B nC n D n j
    
    
A B C D j

Differentiating gives us
dn A dn B dn C dn D dn j (a)
d     
A B C D j

We know 1 dn j
rj  or dn j  r V dt
V dt j
Hence, dn A  rAV dt
Substituting to equation ( a ) gives us
 r AVdt rB Vdt rC Vdt r Vdt r j Vdt
   D 
A B C D j

or r r r r
A  B  c  D
   
A B C D

This allow us, if we know the rate of one species, it is possible to

know the rate of the others. i.e we can relate the rate productions
of the individual components.
Consider a reaction proceeding as per Stoichiometric formula,

 A A  B B   C C  D D
For a stoichiometrically single reaction, that obeys the law of definite
proportions, the rate of production of various reactants and products are
related through stoichiometry as

rA rB rC rD
  
 A  B C D

Notice that 1 dn j
rj 
V dt
Thus the rate of change of moles of one chemical species is related to
the other can be represented by the following relationships

1 1 dn A 1 1 dn B 1 1 dn C 1 1 dn D
   
 A V dt  B V dt  C V dt  D V dt
or for constant volume

1 dC A 1 dC B 1 dC C 1 dC D
   
 A dt  B dt  C dt  D dt
 1.2.2 The rate of reaction (The species – independent rate)

Recalling the rate of production from material balance for batch

reactor
1 dn j
rj 
V dt
or
dn j  r V dt
j dn j
d 

j
Substituting to equation (2.5) and
rearranging gives
 j d
r 
j V dt
 or r
j  1 d
 j V dt
Since extent of reaction is independent of reactants
and products automatically the ratio

r
j

j
is also independent of species (products and
reactants), i.e. independent of the type of the system
(i.e., batch or continuous flow)
This ratio is called the rate of reaction (species–
independent rate) which is described in
r
r j

j
where

r is the rate of reaction (species – independent rate) it must

be the same for all chemical species participating in the
reaction

r is the rate of production of chemical species j per unit

j volume.
 The major disadvantage of species –dependent
rate(the rate of production) definition is that the
rates of various species in one chemical
reaction are different if their stoichiometric
coefficients are different.

For the reaction

 A A  B B   C C  D D
Because of stoichiometric coefficients difference, the rates of
various species are different as we see
rA rB rC rD
  
 A  B C D
 The major advantage of species –independent
rate( rate of reaction) is that the reaction rate is
referenced to the reaction itself, rather than to a
species
But note that, the value of r is not the same for different
reactions
N2 + 3H2 = 2NH3
As it is for
½ N2 + 3/2H2 = NH3

Because the stoichiometric coefficients are not

the same in these two reactions.
The rate of reaction (species – independent rate) is solely a function
of the properties of the reacting materials (e.g. species
concentration, temperature, pressure etc.) and is independent of
species and the type of the system (i.e., batch or continuous flow)

Taking equation dCj

rj 
dt
rearranged rj 1 dCj (2.6.2)
r  
j  j dt
where

r is the rate of reaction and

r is the rate of production of chemical
j species j per unit volume.
In general, the rate of reaction r r
j
and the rate of production, r r
j 
j
have the following relationship:
a) Simple reaction rj  j r
or 1 dn j
  jr
V dt
b) Multiple reactions R
rj    i , j ri
i 1
or
1 dn j R
   i , j ri
V dt i 1
 For constant volume dC j
  jr
dt
dC j R
   i , j ri (2.11)
dt i 1
It is worth mentioning again here that the rate expression cannot be changed
when using a batch or continuous system provided the concentration are
unchanged. Thus, as illustration equation (2.11) will be used similarly for different

rj  j r
systems

dC j dF j F j,0 - F j
   j r
dt dV -V
 R
rj    i , j ri
i 1

dC j dF j F j,0 - F j R
     i, j ri
dt dV -V i 1
Using this considerations, simple reaction
A  P
can be written for different system similar to equation (2.6.2)
- FA
1 dC A 1 dFA 1 F A,0
r   
 A
dt  dV A
 A
-V
or
dC A dFA F A,0 - FA
   Ar
dt dV -V
Ex.1 For the following reactions, find the rate formation of species A,B,C,D
and E for a batch reactor
r1 r4
A B D
r2 r3

r5
E C

dC j dCB
R  r1  r3  r4
   i , j ri dt
dt i 1
dCC
dC A  r2  r3  r5
 r1  r2 dt
dt
dCE
dCD  r5
 r4 dt
dt
 Rate of Reaction, r
Based on the experimental evidence, Depends on the number of
parameters
• the nature of the species involved in the reaction;
• Concentrations of species;
• Temperature;
• Catalytic activity;
• pH
• Nature of contact of reactants; and
• Wave-length of incident radiation
• The nature of the species involved in the reaction
Examples of types of very fast reactions involve ions in
solution, such as the neutralization of a strong acid by a
strong base, and explosions.
.
•Concentrations of species
Rate of reaction usually depends on concentration of
reactants (and sometimes of products), and usually
increases as concentration of reactants increases. Thus,
many combustion reactions occur faster in pure oxygen
than in air at the same total pressure.

•Temperature
Rate of reaction depends on temperature and usually increases
nearly exponentially as temperature increases.
•Catalytic activity
Many reactions proceed much faster in the presence of a
substance which is itself not a product of the reaction. This
is the phenomenon of catalysis, and many life processes
and industrial processes depend on it.

•Nature of contact of reactants

The nature or intimacy of contact of reactants can greatly affect
the rate of reaction. Thus, finely divided coal burns much
faster than lump coal.
 Wave-length of incident radiation
Some reactions occur much faster if the reacting
system is exposed to incident radiation of an
appropriate frequency.

Note that
 the rate of reaction depends on the above
parameters and is expressed mathematically in
the form of a kinetic law /rate law;
that is, for species A in a given reaction, is a function of
the concentration of all components
participating in the reaction, C ; the
temperature, T ; the pressure, P ; catalyst
variables and other parameters, S :

r = function (C; T; P; Cat. variables) (2.13)

Rate equation
(kinetic law /rate law)
  The form of the Rate equation (kinetic law /rate
law) must be established by experiment, and the
complete expression may be very complex and, in
many cases, very difficult, if not impossible, to
formulate explicitly.
r = k(Cj) (2.13.1)
Where: k constant of proportionality and incorporates
all the variables other than concentration.

It is defined as the
 specific reaction rate or more.
 commonly the reaction velocity constant, or
 reaction rate constant.
The reaction rate constant as a function of temperature
is expressed by Arrhenius equation

k  Ae - E RT (2.14)
where
A is, termed the frequency factor,
E is activation energy, and is also usually assumed
independent of temperature
R is the gas law constant and
T is the absolute temperature
Activation energy
 is defined as the energy that must be overcome in
order for a chemical reaction to occur.
Cont’d …….Activation energy
 may also be defined as the minimum energy required
to start a chemical reaction.
 can be thought of as the height of the potential
barrier (sometimes called the energy barrier)
separating two minima of potential energy (of the
reactants and products of a reaction).

For a chemical reaction to proceed at a reasonable rate,

there should exist an appreciable number of molecules
with energy equal to or greater than the activation
energy.
The Arrhenius equation gives the relationship between the activation
energy and the rate at which a reaction proceeds.

k  Ae - E RT

While this equation suggests that the activation energy is

dependent on temperature, in regimes in which the Arrhenius
equation is valid this is cancelled by the temperature dependence
of k.
Thus, Ea can be evaluated from the reaction rate coefficient at any
temperature (within the validity of the Arrhenius equation).
The highest energy position (peak position) represents the
transition state. the energy required to enter transition state
decreases, thereby decreasing the energy required to initiate the
reaction.
 We can conclude here the reaction rate is affected
Notice here

not only by the concentration of species in the

reacting system but also by the temperature.

 An increase in temperature will almost

always result in an increase in the rate of
reaction;
in fact, the literature states that, as a general rule, a
100C increase in reaction temperature will double the
reaction rate constant.
Hence
r = f1 (temperature) f2(concentration) (2.13.2)

In the rate expression (rate equation) the influence of

concentration and temperature are usually expressed
separately. The following topics demonstrate the
influence of these parameters on the rate of reaction.
2.2 The effect of concentration on rate of reaction
 If the temperature of the system is maintained constant, then the rate of
reaction is determined by the concentrations of the substances making up
the system and depend hyperbolically on the reactant concentration

Rate

Reactant Concentration
 A mathematical formula that describes the rate to the
concentration is termed the rate equation or the kinetic
equation.
 The rate of any reaction is at each instant proportional
to the product of the concentration of the reactants, with
each concentration raised to power.
Hence, a mathematical formula (rate equation or the
kinetic equation. ) that describes the reaction rate to the
concentration for irreversible reaction using equation
(2.13.2) may assume the following form:

  
r  kC j C  C  ...... (2.15)

The basic laws of kinetics follows from a large body of

experimental data and express dependence of the reaction rate
on concentration:
where
k is the proportionality constant and is called the reaction rate
constant that is independent of concentration, markedly
influenced by the temperature and may be subject to the influence
of pressure, pH, kinetic isotopes, and the presence of catalysts
 ,  ,   are orders of reaction with respect to
individual reacting components
The orders of the reaction shows that the manner in which the
reaction rate varies with the concentrations of the reactants and
products or
 the reaction order is the exponent in the rate equation or the power
to which the concentration or partial pressure must be raised to fit the
data
The overall order of reaction (R) refers to the sum of
R       ........
The overall order of reaction does not have to be an integer and may
be determined empirically.
In studying kinetics, reactions are classified according to the order
of reaction as elementary and non- elementary reaction.

Elementary reaction is a reaction where the order of reaction is

proportional to the stoichiometric coefficient of reactant concentration

Consider the reaction aA  bB  cC  dD

if stoichiometric amounts of A and B are initially present,
the reaction will proceed to the right until all the A and B
have reacted (disappeared) and C and D have been formed.
If the reaction is elementary, the rate of the above
reaction is given by

r k a
CA b
CB
 The rate of reaction like reaction rate
constant, must refer to one of the species in the
reacting system. r  k Ca Cb
A A A B
This notation is account for the reaction or formation of A

Here a is the order of the reaction with respect to A, and b is the

order with respect to B. That is stoichiometry coefficient is
identical to the order of reaction.
An example of such reaction is

H 2  I 2  2 HI r  k C C
I I H
2 2 2

  (rA )  kC A
2   (rA )  kC A2
   (rA )  kC A C B
3   (rA )  k C A3
    C  (rA )  kC A C B CC
Fig. Rate versus concentration graphs for zero, first, and
second order reactions.
Elementary reactions are often represented by an
equation showing both the molecularity and the rate
constant.
Molecularity
For example, a bimolecular irreversible reaction
2 A 2R (a)
second-order represents with rate constant k implying that the rate of
reaction is
(r )  r  k C2
A R 2 A
It would not be proper to write eq. (a) as A R
for this would imply that the rate expression is
(r )  r  k C
A R 1 A
Rate constant
We should note that writing the elementary reaction with the rate constant,
as shown by Eq. (a), may not be sufficient to avoid ambiguity /confusion/.
At times it may be necessary to specify the component in the reaction to
which the rate constant is referred. For example, consider the
reaction
B  2D  3T (b)
If the rate is measured in terms of B, the rate equation

(r ) k C C 2
B B B D
If it refers to D, the rate equation is
(r ) k C C 2
D D B D
Or if it refers to the product T, then r  k C C2
T T B D
But from the stoichiometry (r )   1 r  1r
B 2 D 3T
k C C 2  1 k C C 2  1k C C 2
B B D 2 D B D 3T B D

or k  1 k  1k
B 2 D 3T
In Eq. (b), which of these three k values are we
referring to? We cannot tell.
Hence, to avoid ambiguity when the stoichiometry
involves different numbers of molecules of the various
components, we must specify the component being
considered.
The order of reaction may be integers or fractions
and may be values of
 Positive integers,
 Negative integers,
 Fractions
 as well as zero
A fraction order reaction
The reaction CH 3 CHO  CH 4  CO


d CCH 3 CHO
dt

 k CCH 3 CHO 2
3
 Zero order reaction
Zero-order reaction for one reactant
If the reaction order is zero for one reactant, it means
that the rate is independent of the reactant
concentration, at least for the range of concentrations
covered in the tests. dC
 A  k C 0 k
dt 0 A 0
It does not mean that the reaction can take
place at zero reactant concentration.
Zero order to A may indicate that the overall reaction
requires several steps, and the rate-limiting step does
not involve A.
However, at very low values of CA, some step
involving A will become important or controlling,
and the reaction order for A will change to a positive
value.
For a two-phase reaction system, such as
A + B(gas) = C,
mass transfer of B could be the rate-limiting step,
making the reaction appear zero order to A over a
wide range of concentrations.

Negative orders reactions

A negative order for a particular substance
signifies that the rate decreases (is inhibited) as
the concentration of that substance increases.
Such type of orders

 are sometimes observed for bimolecular reactions on

solid catalysts.
 Increasing the partial pressure of one reactant, A, which
is strongly adsorbed, can lead to a surface mostly
covered with adsorbed A, leaving little space for
adsorption of reactant B and make negative order to A.
 However, the negative order for A would change to zero
order and then to a positive order as the partial pressure
of A is reduced to very low values.
Overall order of reaction

When the order of reactions are integers or half-integer values,

such as n= 1, n=2/1, n=2.2, they may offer clues about the
mechanism of the reaction.
For example, A +B = C
if the gas-phase reaction of A with B appears to be first order to A
and first order to B, this is consistent with the collision theory. The
number of collisions per unit volume per unit time depends on the
product of the reactant concentrations, and a certain fraction of the

collisions will have enough energy to cause reaction.

 This leads to the following equation:
r = kCACB
If the rate data fit this expression, the reaction is described as first
order to A and first order to B. But calling the reaction second
order is ambiguous, since a total order of 2 could mean

r = kCA1.5 CB0:5
or
r = kCA0CB2
To sum up, the condensed form of expressing
the rate can be ambiguous /unclear/.
To eliminate any possible confusion, write
 the stoichiometric equation followed
by the complete rate expression, and
give the units of the rate constant.
 Non-elementary reaction
is a reaction where the order and stoichiometric
coefficient are not to be equal.
For example, in the following reaction,

H 2  Br2  2 HBr

dCHBr k1 CH 2 CBr2
rHB  
r dt CHBr
k2 
CBr2
Product Species in the Rate Law
Rate of reaction may depend on the concentration of a product
The possible involvement of product species in the rate law should
be considered in the experimental investigation. This can be tested
by measuring the rate at low conversions.
Two meaning based on the order of reaction
 If the order of reaction for a product is negative, the effect is
called product inhibition, and is common in catalytic
reactions.
 If the order of reaction for a product is positive, the reaction
accelerates with increasing conversion, and the effect is
called autocatalysis.
 The Unit of the rate constant
The units of the reaction rate constant k vary with the overall order of the

reaction.
These units are those of a rate divided by the nth power of
concentration as evident from Equations
(r )  kC n
A A
(r ) moles (volume)(time)
k A 
Cn (moles volume)n
 n 1
k  (time)1 moles
 
 
 
 
volume 
Consider a reaction involving a reactant such that
A → Products
 

k  moles 1
 
Zero – order: n=0 



m3 s





First – order: n=1 1
k  


s 



m 3
k
Second – order: n=2 (moles)(s)
Table: Units of rate constant
Rate defined in Partial Pressure
 Alternatively, we may redefine the rate of reaction in terms of the rate of change of the
partial pressure of a substance

Consider  S
Rate in terms of partial pressure we have
dC 1 dP
(r )   A   A  kC
A dt RT dt A P  C RT
A A
Substitution we get P
dC 1 dP
(r )   A   A  k A
A dt RT dt RT
dP
(r )   A  k p P
A,P dt A
 For two components, aA  bB  P
we get
dP
(r )   A  k p Pa Pb
A,P dt A B

 The order of reaction is unchanged for a

change of parameter.
First – order reaction  S

 rA  kC C A  k P PA
kC and k P rate constants in terms of concentration and
partial pressure, but their unit is also different.
The rate of reaction has the same units whether
concentration or partial pressures are used
 rA  kc C A  k p PA
 mol   1   mol  1 mol 
 rA    kc      kp  atm
 s m3   s   m3   s m3 atm 

kc has a dimension 1 
 s 
1 mol 1 
k p has a dimension  s . 3 . atm 
 m 
Ex.2. For a gas reaction at 400k the rate is reported to

a) What are the units of the rate constant?

b) What is the value of the rate constant for this
reaction if the rate equation is expressed as
Rate of Reaction and Rate of Production of each species using
(kinetic law /rate law):- Rate of Reaction has a relation with Rate
r
of Formation as
j r  k(C ) (C )  (C )   
 A B C
j
Consider the reaction
2A B + 3C r  k C2A

The rate for the reaction is

r A rB rC
r     kC 2 A
2 1 3
r A   2kC 2 A   k AC 2 A

rB  kC 2 A  k BC 2 A

rC  3kC 2 A  kC C 2 A
Consider the reaction
2N2O5 2N2O4 + O2

rN O rN O rO
r  2 5  2 4  2  kC 2 N O
2 2 1 2 5
dC N O dC N O dC O
1 2 5 1 2 4 2 2
    kC N O
2 dt 2 dt dt 2 5
2 2
rN O  2k N O C N O  kC N O
2 5 2 5 2 5 2 5

rN O  2k N O C 2 N O  kC 2 N O
2 4 2 4 2 5 2 5
2 2
rO  k O C N O  kC N O
2 2 2 5 2 5
Ex. 3. For the following elementary reactions, find the formation of
species A,B,C,D and E for a batch reactor
k1 k4
A B D
dC j R
 i , j ri
k2 k3

k5  
E C dt i 1
dC A
  k1C A  k2C A  (k1  k2 )C A
dt
dC B
 k1C A  k3C B  k4C B  k1C A  C B ( k3  k4 )
dt
dCC
 k2C A  k3C B  k5C E
dt
dC D
 k4C B dC E
  k5C E
dt dt
Notice, Rate of reaction
- can not be changed using a batch or continuous system
provided the order of reaction and concentration are unchanged

dC A dFA FA,0  FA
rA      k C C A   k P PA
dt dV V

2.3 Effects of temperature on the rate of reaction

Generally, the vast majority of the chemical reaction rate of reaction
increases rapidly with the rise of temperature. This is one of the
reasons that heating is often used in a chemical process. According to a
general rule, an increase of 100 in temperature results in a 2- to 4-
fold increase the rate of reaction. Looking for any type of chemical
reaction, the kinetic law for the rate of reaction is determined by the
product.
 r  k(CA ) (CB )      (2.20)
Equation (2.20) can be demonstrate for the rate of reaction as a function of both
concentration and temperature as

r  Ae- E RT  
(CA ) (CB )     (2.20.1)
Generally, from the equation (2.20.1), changing the temperature may, in
principle,
 has an effect on concentration,
the order of reaction
 and the rate constant.

Since the exponential term is much more temperature-sensitive,

we can reasonably consider the rate constants /rate of reaction to
vary approximately as e-E/RT
That is why, Experiment confirmed that the temperature
change has insignificant effect on the concentration and
order of reaction to change the rate of reaction.

Hence, the rate constant is affected most strongly by temperature:

that is why, when speaking of the effect of temperature on the rate of
reaction, one usually implies the change of rate constant.

Rate constant as a function of Temperature is described using

Arrhenius equation as :

k  A e- E RT
The dependency of the rate on temperature is shown for different
types of reactions in Figure 2.3
 1
Rate 3

Temperature
Figure 2.3 Reaction rate as a function of temperature:
1- single forward reaction,2- equilibrium reaction, 3-
solid catalyzed reaction
Activation Energy, E was considered by Arrhenius as the
amount of energy that a reacting system must have in excess
of the average initial energy level of reactants to enable the
reaction to proceed.

Activation energy is determined using Arrhenius equation as

ln k  
E  1   ln 
 
R T 
1
- A plot of ln k vs gives a straight line,
T
1 E
ln k taken against , yields a slope equal to  .
T R
Figure : Temperature dependency of a reaction according
to Arrhenius' law.

The magnitude of Activation energy depends on the slope of

the curve
ln k
Low E

High E E
tan α = -
R

1
T
From the Figure, a large slope obtained for large
E and small slope for small E
 Reactions with high activation energies are
very temperature sensitive
 Reactions with low activation energies are
relatively temperature–insensitive
 A given reaction is much more temperature-
sensitive at low temperatures than at high
temperature.
Ex.4. The following data were obtained from experiment

Using the data, calculate the activation energy and

frequency factor, and the value of rate constant, k at
T = 328K
Considering equation (2.20.1)
1 2
r  Ae - E RT
(CA ) (CB )     (2.20.1)
If the rate constant is found at two different temperatures and,
we have for the same concentration , order of reaction and E
stays constant
r2 k2 E  1 1 
ln  ln   - 
r1 k1 R T1 T 2 
The activation energy may be calculated from the rate constant at
two distinct but adjacent temperature T1 and T2 as follows
- E RT 2
k1  A e
- E RT1
k2  Ae
Combining the two equations, we obtain
 k2
ln ( )
k1
ER
1  1
T1 T2

The activation energy has been equated to the energy

needed by colliding molecules for reaction to occur.
 Example 5.
How much does a reaction rate with an activation energy of
15,000 cal/mole vary when the temperature is increased from
300 to 310 K? From 300 to 400 K?
The ratio of the rate of this reaction at 310 K to that at 300 K
,

k 310 e -E/RT2
exp- 15,000 / (2 x 310)
  E / RT1   2.24
k 300 e exp- 15,000 / (2 x 300)

Between 300 and 400 K this ratio is very large

k 400 e -E/RT2 exp- 15,000 / (2 x 400)

  E / RT1   517
k 300 e exp- 15,000 / (2 x 300)
Ex.8. The pyrolysis of ethane proceeds with an
activation energy of about 300kJ/mol. How much
faster is the decomposition at 650℃ than at 500℃?
Ex.9. On doubling the concentration of reactant,
the rate of reaction triples. Find the reaction order.
Ex.11. Milk is pasteurized if it is heated to 63℃ for 30
min, but if it is heated to 74°C it only needs 15 s for the
same result. Find the activation energy of this
sterilization process.
Ex.12. At 500 K the rate of a bimolecular
reaction is ten times the rate at 400 K. Find
the activation energy of this reaction and
what is the percentage difference in rate of
reaction at 600 K.