Chemical Reaction Engineering

KINETICS OF HOMOGENEOUS REACTIONS

Homogeneous and Heterogeneous systems

A reaction is homogeneous if it takes place in one phase alone. A reaction is heterogeneous if

it requires the presence of at least two phases to proceed at the rate that it does. It is
immaterial whether the reaction takes place in one, two, or more phases; at an interface; or
whether the reactants and products are distributed among the phases or are all contained
within a single phase. All that counts is that at least two phases are necessary for the reaction
to proceed as it does.

Examples where classification is not clear cut

(i) Large class of biological reactions, the enzyme-substrate reactions.

Here the enzyme acts as a catalyst in the manufacture of proteins and other products.
Since enzymes themselves are highly complicated large-molecular-weight proteins of
colloidal size, 10-100 nm, enzyme-containing solutions represent a gray region
between homogeneous and heterogeneous systems.

(ii) Very rapid chemical reactions, such as the burning gas flame.

Here large non-homogeneity in composition and temperature exist. Strictly speaking,

then, we do not have a single phase, for a phase implies uniform temperature, pressure,
and composition throughout.

Classification of Chemical Reactions Useful in Reactor Design

Non-Catalytic Catalytic
Homogeneous Most gas phase reactions Most Liquid phase reactions
Fast reactions such as burning of Reactions in colloidal systems,
Heterogeneous a flame enzyme and microbial systems
Burning of coal Ammonia synthesis
Roasting of ores Oxidation of ammonia to produce
Attack of solids by acids nitric acid
Gas-liquid absorption with Cracking of crude oil
reaction Oxidation of SO2 to SO3
Reduction of iron ore to iron and
steel

Definition of Reaction Rate

Rate of reaction is defined in a number of ways, all interrelated and all intensive rather than
extensive measures.

We select one reaction component for consideration and define the rate in terms of this
component “i”. If the rate of change in number of moles of this component due to reaction is
dN/dt, then the rate of reaction in its various forms is defined as follows.

Kinetics of Homogeneous Reactions Page 1

 Chemical Reaction Engineering

Based on unit volume of reacting fluid,

1 𝑑𝑁𝑖 (moles of "i" formed)

𝑟𝑖 = = … … … … … … … … … … … . (𝑖)
𝑉 𝑑𝑡 (volume of fluid)(time)

Based on unit mass of solid in fluid-solid systems,

1 𝑑𝑁𝑖 (moles of "i" formed)

𝑟′𝑖 = = … … … … … … … … … … … . (𝑖𝑖)
𝑊 𝑑𝑡 (mass of solid)(time)

Based on unit interfacial surface in two-fluid systems or based on unit surface of solid in gas-
solid systems,

1 𝑑𝑁𝑖 (moles of "i" formed)

𝑟′′𝑖 = = … … … … … … … … … … … (𝑖𝑖𝑖)
𝑆 𝑑𝑡 (surface)(time)

Based on unit volume of solid in gas-solid systems

1 𝑑𝑁𝑖 (moles of "i" formed)

𝑟′′′𝑖 = = … … … … … … … … … . . (𝑖𝑣)
𝑉𝑠 𝑑𝑡 (volume of solid)(time)

Based on unit volume of reactor, if different from the rate based on unit volume of fluid,

1 𝑑𝑁𝑖 (moles of "i" formed)

𝑟′′′′𝑖 = = … … … … … … … . . (𝑣)
𝑉𝑟 𝑑𝑡 (volume of reactor)(time)

In homogeneous systems the volume of fluid in the reactor is often identical to the volume of
reactor. In such a case 𝑉 and 𝑉𝑟 are identical and Eqs. (i) and (v) are used interchangeably. In
heterogeneous systems all the above definitions of reaction rate are encountered, the
definition used in any particular situation often being a matter of convenience.

From Eqs. (i) to (v) these intensive definitions of reaction rate are related by

𝑉𝑟𝑖 = 𝑊𝑟′𝑖 = 𝑆𝑟′′𝑖 = 𝑉𝑠 𝑟′′′𝑖 = 𝑉𝑟 𝑟′′′′𝑖

The Rate Equation

Suppose a single-phase reaction aA + bB  rR + sS. The most useful measure of reaction rate
for reactant A is then

Kinetics of Homogeneous Reactions Page 2

 Chemical Reaction Engineering

In addition, the rates of reaction of all materials are related by

−𝑟𝐴 −𝑟𝐵 𝑟𝑅 𝑟𝑆
= = =
𝑎 𝑏 𝑟 𝑠

Experience shows that the rate of reaction is influenced by the composition and the energy of
the material. By energy we mean the temperature (random kinetic energy of the molecules),
the light intensity within the system (this may affect the bond energy between atoms), the
magnetic field intensity, etc. Ordinarily we only need to consider the temperature, so let us
focus on this factor. Thus, we can write

Single and Multiple Reactions

When a single stoichiometric equation and single rate equation are chosen to represent the
progress of the reaction, we have a single reaction.

When more than one stoichiometric equation is chosen to represent the observed changes,
then more than one kinetic expression is needed to follow the changing composition of all the
reaction components, and we have multiple reactions.

Multiple reactions may be classified as:

Series reactions,

ARS

Parallel reactions, which are of two types

and more complicated schemes, an example of which is

A+BR
R+BS
Here, reaction proceeds in parallel with respect to B, but in series with respect to A, R, and S.

Kinetics of Homogeneous Reactions Page 3

 Chemical Reaction Engineering

Elementary and Non-elementary Reactions

Consider a single reaction with stoichiometric equation

A+BR

If we postulate that the rate-controlling mechanism involves the collision or interaction of a

single molecule of A with a single molecule of B, then the number of collisions of molecules A
with B is proportional to the rate of reaction. But at a given temperature the number of
collisions is proportional to the concentration of reactants in the mixture; hence, the rate of
disappearance of A is given by

−𝑟𝐴 = 𝑘 𝐶𝐴 𝐶𝐵

Such reactions in which the rate equation corresponds to a stoichiometric equation are called
elementary reactions.

When there is no direct correspondence between stoichiometry and rate, then we have non-
elementary reactions. The classical example of a non-elementary reaction is that between
hydrogen and bromine,

H2 + Br2  2HBr

which has a rate expression

𝑘1 [𝐻2 ] [𝐵𝑟2 ]1/2

𝑟𝐻𝐵𝑟 =
[𝐻𝐵𝑟]
𝑘2 + [ ]
𝐵𝑟2

Non-elementary reactions are explained by assuming that what we observe as a single

reaction is in reality the overall effect of a sequence of elementary reactions. The reason for
observing only a single reaction rather than two or more elementary reactions is that the
amount of intermediates formed is negligibly small and, therefore, escapes detection.

Molecularity and Order of Reaction

The molecularity of an elementary reaction is the number of molecules that come together to
react in an elementary reaction and is equal to the sum of stoichiometric coefficients of
reactants in this elementary reaction. This has been found to have the values of one, two, or
occasionally three. Note that the molecularity refers only to an elementary reaction.

Often we find that the rate of progress of a reaction, involving, say, materials A, B, …….., D, can
be approximated by an expression of the following type:

−𝑟𝐴 = 𝑘 𝐶𝐴𝑎 𝐶𝐵𝑏 … … … 𝐶𝐷𝑑 , 𝑎 + 𝑏 + ⋯…+ 𝑑 = 𝑛

where a, b, . . . , d are not necessarily related to the stoichiometric coefficients.

We call the powers to which the concentrations are raised the order of the reaction. Thus, the
reaction is

Kinetics of Homogeneous Reactions Page 4

 Chemical Reaction Engineering

ath order with respect to A

bth order with respect to B
nth order overall

Since the order refers to the empirically found rate expression, it can have a fractional value
and need not be an integer. However, the molecularity of a reaction must be an integer
because it refers to the mechanism of the reaction, and can only apply to an elementary
reaction.

Rate Constant ‘k’

When the rate expression for a homogeneous chemical reaction is written in the form of

−𝑟𝐴 = 𝑘 𝐶𝐴𝑎 𝐶𝐵𝑏 … … … 𝐶𝐷𝑑 , 𝑎 + 𝑏 + ⋯…+ 𝑑 = 𝑛

the dimensions of the rate constant k for the nth-order reaction are

(𝑡𝑖𝑚𝑒)−1 (𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 )1−𝑛

which for a first-order reaction becomes simply (𝑡𝑖𝑚𝑒)−1

Representation of an Elementary Reaction

In expressing a rate we may use any measure equivalent to concentration (for example,
partial pressure), in which case

𝑟𝐴 = 𝑘 𝑝𝐴𝑎 𝑝𝐵𝑏 … … … 𝑝𝐷𝑑 , 𝑎 +𝑏 +⋯…+𝑑 = 𝑛

Whatever measure we use leaves the order unchanged; however, it will affect the rate
constant k.

For brevity, elementary reactions are often represented by an equation showing both the
molecularity and the rate constant. For example,

𝑘1
2𝐴 → 2𝑅

represents a biomolecular irreversible reaction with second-order rate constant k1 implying

that the rate of reaction is

−𝑟𝐴 = 𝑟𝑅 = 𝑘1 𝐶𝐴2

We should note that writing the elementary reaction with the rate constant, may not be
sufficient to avoid ambiguity. 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

If the rate is measured in terms of B, the rate equation is

−𝑟𝐵 = 𝑘𝐵 𝐶𝐵 𝐶𝐷2

Kinetics of Homogeneous Reactions Page 5

 Chemical Reaction Engineering

If it refers to D, the rate equation is

−𝑟𝐷 = 𝑘𝐷 𝐶𝐵 𝐶𝐷2

Or if it refers to the product T, then

𝑟𝑇 = 𝑘 𝑇 𝐶𝐵 𝐶𝐷2

But from the stoichiometry

1 1
−𝑟𝐵 = 𝑟𝐷 = 𝑟𝑇
2 3
hence,

1 1
𝑘𝐵 = 𝑘𝐷 = 𝑘 𝑇
2 3
Representation of a Non-elementary Reaction

A non-elementary reaction is one whose stoichiometry does not match its kinetics.

For example,

𝑁2 + 3𝐻2 ⟷ 2𝑁𝐻3

[𝑁2 ][𝐻2 ]3/2 [𝑁𝐻3 ]

𝑟𝑁𝐻3 = 𝑘1 − 𝑘 2
[𝑁𝐻3 ]2 [𝐻2 ]3/2

This non-match shows that we must try to develop a multistep reaction model to explain the
kinetics.

Temperature-Dependent Term of Rate Equation – Temperature Dependency from

Arrhenius' Law

For many reactions, and particularly elementary reactions, the rate expression can be written
as a product of a temperature-dependent term and a composition dependent term, or

𝑟𝑖 = 𝑓1 (𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 ). 𝑓2 (𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 )
= 𝑘. 𝑓2 (𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 )

For such reactions the temperature-dependent term, the reaction rate constant, has been
found in practically all cases to be well represented by Arrhenius' law:

𝑘 = 𝑘0 𝑒 −𝐸/𝑅𝑇

where 𝑘0 is called the frequency or pre-exponential factor and E is called the “activation
energy of the reaction." This expression fits experiment well over wide temperature ranges
and is strongly suggested from various standpoints as being a very good approximation to the
true temperature dependency.

Kinetics of Homogeneous Reactions Page 6

 Chemical Reaction Engineering

At the same concentration, but at two different temperatures, Arrhenius' law indicates that

𝑟2 𝑘2 𝐸 1 1
𝑙𝑛 = 𝑙𝑛 = ( − )
𝑟1 𝑘1 𝑅 𝑇1 𝑇2

provided that E stays constant.

Comparison of Theories with Arrhenius' Law

The expression

𝑘 = 𝑘′0 𝑇 𝑚 𝑒 −𝐸/𝑅𝑇 , 0≤𝑚 ≤1

summarizes the predictions of the simpler versions of the collision and transition state
theories for the temperature dependency of the rate constant. For more complicated versions
m can be as great as 3 or 4. Now, because the exponential term is so much more temperature-
sensitive than the pre-exponential term, the variation of the latter with temperature is
effectively masked, and we have in effect.

𝑘 = 𝑘0 𝑒 −𝐸/𝑅𝑇

Figure: Sketch showing temperature dependency of the reaction rate.

Kinetics of Homogeneous Reactions Page 7

 Chemical Reaction Engineering

The temperature dependency of reactions is determined by the activation energy and

temperature level of the reaction, as illustrated in Figure above.

These findings are summarized as follows:

1. From Arrhenius' law a plot of ln k vs 1/T gives a straight line, with large slope for large E
and small slope for small E.

2. Reactions with high activation energies are very temperature-sensitive; reactions with
low activation energies are relatively temperature-insensitive.

3. Any given reaction is much more temperature-sensitive at a low temperature than at a

high temperature.

4. From the Arrhenius law, the value of the frequency factor k, does not affect the
temperature sensitivity.

For multiple reactions a change in the observed activation energy with temperature indicates
a shift in the controlling mechanism of reaction.

Thus, for an increase in temperature,

 Eobs rises for reactions or steps in parallel,
 Eobs falls for reactions or steps in series.

Conversely, for a decrease in temperature

 Eobs falls for reactions in parallel,
 Eobs rises for reactions in series.

These findings are illustrated in Figure.

Figure: A change in activation energy indicates a shift in controlling mechanism of reaction.

Kinetics of Homogeneous Reactions Page 8

 Chemical Reaction Engineering

Problem – 1

Solution

Problem – 2

Solution

Kinetics of Homogeneous Reactions Page 9

 Chemical Reaction Engineering

Problem – 3

Solution

Problem – 4

Solution

Problem – 5

Kinetics of Homogeneous Reactions Page 10

 Chemical Reaction Engineering

Solution

Problem – 6

Solution

Problem – 7

Find the expression for rate of reaction

Kinetics of Homogeneous Reactions Page 11

 Chemical Reaction Engineering

Solution

Problem – 8

Solution

Kinetics of Homogeneous Reactions Page 12

 Chemical Reaction Engineering

Problem – 9 (Gate 2016)

Solution

Problem – 10 (Gate 2016)

Kinetics of Homogeneous Reactions Page 13

 Chemical Reaction Engineering

Solution

Problem – 11 (Gate 2015)

Solution

Problem – 12 (Gate 2015)

Kinetics of Homogeneous Reactions Page 14

 Chemical Reaction Engineering

Solution

Problem – 13 (Gate 2013)

Solution

Kinetics of Homogeneous Reactions Page 15

 Chemical Reaction Engineering

Problem – 14 (Gate 2011)

Kinetics of Homogeneous Reactions Page 16

 Chemical Reaction Engineering

Solution

Problem – 15 (Gate 2007)

Kinetics of Homogeneous Reactions Page 17

 Chemical Reaction Engineering

Solution

Problem – 16 (Gate 2005)

Solution

Kinetics of Homogeneous Reactions Page 18

 Chemical Reaction Engineering

Problem – 17 (Gate 2005)

Solution

Problem – 18 (Gate 2005)

Kinetics of Homogeneous Reactions Page 19

 Chemical Reaction Engineering

Solution

Problem – 19 (Gate 2004)

Kinetics of Homogeneous Reactions Page 20

 Chemical Reaction Engineering

Problem – 20 (Gate 2004)

N2 + 3H2 NH3

Solution

Correct answer is (c)

Because the rate expression does not depend on how we write the stoichiometry of the
reaction. It is experimentally determined expression.

Kinetics of Homogeneous Reactions Page 21

 Chemical Reaction Engineering

Problem – 21 (Gate 2003)

Solution

Kinetics of Homogeneous Reactions Page 22

 Chemical Reaction Engineering

Problem – 22 (Gate 2002)

Solution

Kinetics of Homogeneous Reactions Page 23

 Chemical Reaction Engineering

Problem – 23 (Gate 2001)

Solution

Problem – 24 (Gate 2000)

Kinetics of Homogeneous Reactions Page 24

 Chemical Reaction Engineering

Solution

Correct: (A)

Problem – 25 (Gate 1999)

Solution

Correct: (B)

Problem – 26 (Gate 1998)

Solution

Correct: (C)

Problem – 27 (Gate 1998)

Solution

Correct: (D)

Problem – 28 (Gate 1993)

Solution

Arrhenius Theory: m = 0
Collision Theory: m = ½
Transition state theory: m = 1

Kinetics of Homogeneous Reactions Page 25

 Chemical Reaction Engineering

Problem – 29 (Gate 1995)

Problem – 30 (Gate 1993)

Solution

Correct: (A)

Kinetics of Homogeneous Reactions Page 26

 Chemical Reaction Engineering

Problem – 31 (Gate 1990)

Solution

Problem – 32 (Gate 1990)

Solution

D; is unaffected by the presence of catalyst

Problem – 33 (Gate 1991)

Solution

(B) High CB, Any CA

Kinetics of Homogeneous Reactions Page 27

 Chemical Reaction Engineering

Problem – 34 (Gate 1991)

Solution

(C) Decreasing T first and then increasing T

Kinetics of Homogeneous Reactions Page 28