Republic of the Philippines

DR. EMILIO B. ESPINOSA, SR. MEMORIAL STATE COLLEGE

OF AGRICULTURE AND TECHNOLOGY
(Masbate State College)
www.debesmscat.edu.ph
Mandaon, Masbate

Module
1
Fundamentals of
Chemical Kinetics

ChE 321 – Chemical Reaction Engineering

Compiled and Edited by:

Engr. Marco Angelo R. Dejucos

 Fundamentals of Chemical Kinetics

I. Overview:

Consider the figure below for a certain industrial chemical process.

Figure 1. Typical chemical process

It is necessary to design chemical processes in such a way that it will produce a desired product
economically from a variety of starting materials through successive treatment steps. From the figure above,
we can see that raw materials undergo some physical treatment steps to put them in the form that can be
reacted chemically. After which, they are passed through a reactor. From this reactor, the products will
undergo further physical treatment (e.g. separations, purifications, etc) so that the final desired product to be
obtained.
Unit operations involves the study of the design of the equipment for the physical treatment steps. On
the other hand, chemical reaction engineering deals with the design of the equipment for the chemical
treatment step of the process. Economically this may be an inconsequential unit, say a simple mixing tank.
More often than not, however the chemical treatment step is the heart of the process. It may make or break the
process economically.
The design of chemical reactors is probably the one area of interest in engineering that is unique to
chemical engineering. It is this function more than anything else which justifies the existence of chemical
engineering as a distinct branch of engineering.
In chemical reactor design, there are two questions which must be answered:
1. What changes can we expect to occur?
- Concerns with thermodynamics
2. How fast will they take place?
- Concerns with the various rate processes - chemical kinetics, heat transfer, mass transfer, etc.
In this topic we will try to discuss some of the basic concepts involved in chemical kinetics.

Topic Duration: Week 1

II. Learning Objectives:

 Define chemical kinetics
 Classify chemical reactions by order of reaction.
 Classify reactions in terms of reversibility
 Identify factors affecting the rate of reaction.
 Define reaction rate.

Key Points
 Definition of Chemical Kinetics
 Classification of Chemical Reactions
 Factors affecting rate of Reaction
 Definition of Reaction Rate
III. Content Focus

A. Definition of Chemical Kinetics

What is Chemical Kinetics?
Chemical kinetics is the branch of physical chemistry that deals with the rates of chemical reactions.
Chemical kinetics is different from thermodynamics which deals with the direction in which the reaction
occurs but tells nothing about its rate. (Laidler, n.d.). Chemical kinetics is simply the study of the factors that
influence the rate of reaction and the explanations for the rate of reaction. Its study is important for the
following reasons:
1. For physical chemists
- It is a tool used to gain insight into the nature of reacting systems, to understand how chemical bonds
are made and broken, and for estimating their energies and stability
2. For organic chemists
 - Used to provide clues to the structure of organic compounds because of the mode of reaction of
compounds. The relative strengths of chemical bonds and molecular structure of compounds can be
investigated using this tool
3. Combustion and dissolution theories
- Basis of this theories stem from chemical kinetics. Chemical kinetics provides a method to study heat
and mass transfer and suggest methods for tackling rate phenomena in other fields of study
4. For chemical engineers
- The kinetics of a reaction must be known which can be used to make a satisfactory design for
equipment in which these reactions can be done on a technical scale. If the reaction is rapid enough so
that the system is essentially is at equilibrium, the design is very much simplified. Kinetic information
is not needed, and the thermodynamic information is sufficient for the design.

B. Classification of Chemical Reactions

Reactions may be classified in many ways. However, in chemical reaction engineering the most useful
classification is according to number and types of phases involve. They are classified as homogeneous and
heterogeneous.
Homogeneous Reaction
 a reaction that takes place in one phase alone.
Heterogeneous Reaction
 requires the presence of at least two phases to proceed at a rate 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 are that at least two phases are necessary for the reaction to proceed as it
does
This classification is not clear-cut as in large class of biological reaction (e.g. enzyme-substrate reactions).
The classification must depend on which description we think is more useful.
Another classification is whether a reaction uses materials that are neither products nor reactants that change
the rate of reaction. These materials are called catalysts. Catalysts can be present in minute amounts. They act
as go-betweens, which can either hinder or accelerate the reaction process while being modified relatively
slowly if at all.
The table below shows the classification of chemical reactions according to the scheme discussed and some
examples.

Table 1 Classification of Chemical Reactions Useful in Reactor Design (Levenspiel, 1999)

C. Factors Affecting the Rate of Reaction

There are many factors affecting the reaction rate.
In homogeneous systems:
 Temperature
 Pressure
 Composition
In heterogeneous systems
 Rate of mass transfer – due to movement from one phase to another during the reaction
 o Example: in the burning of a coal briquette the diffusion of oxygen through the gas film
surrounding the particle, and through the ash layer at the surface of the particle, can play an
important role in limiting the rate of reaction.
 Rate of heat transfer – depending on the heat released or absorbed during the reaction
o Example: an exothermic reaction taking place at the interior surfaces of a porous catalyst
pellet. If the heat released by reaction is not removed fast enough, a severe nonuniform
temperature distribution can occur within the pellet, which in turn will result in differing point
rates of reaction.
For homogeneous systems, may play an important role in determining the rates of heterogeneous reactions.
These heat and mass transfer effects become increasingly important the faster the rate of reaction, and in very
fast reactions, such as burning flames, they become rate controlling.
D. Definition of Reaction Rate
We can define the rate of reaction in a number of ways, all of which are interrelated and all are intensive
rather than extensive measures. To do this, we must first select one component of the reaction 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 dNildt, then the rate of reaction in
its various forms is defined as follows.
 Based on unit volume of reacting fluid,
1 d Ni moles i formed
r i= = Equation 1
V dt (volume of fluid )(time)
 Based on unit mass of solid in fluid-solid systems,

1 d Ni moles i formed
r 'i= = Equation 2
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 d N i moles i formed

ri = = Equation 3
S dt (surface)(time)
 Based on unit volume of solid in gas-solid systems

''' 1 d Ni moles i formed

ri = = Equation 4
V s dt (volume of solid)(time)

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

''' 1 d Ni moles i formed

ri = = Equation 5
V r 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 Equations 1 and 5 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 Equations 1 to 5 these intensive definitions of reaction rate are related by:

( volume of fluid ) r i=( mass of solid ) r 'i =( surface of solid ) r 'i' = ( volume of solid ) r 'i' ' =(volume of reactor)r 'i ' ' '

Or
' '' '' ' ' '' '
V r i=W r i =S r i =V s r i =V r r i Equation 6

The rate of reaction of a function of the variables of the system

r i=f (system variables)
The form of this functional relationship remains the same, no matter how we choose to define the reaction
rate. It is only the constants of proportionality and their dimensions that change when we switch from one
defining rate equation to another.
Reaction rate

 Defined in terms of the rate with which the products are formed and the reactants are consumed in a
chemical reaction.

Example 1-1

A rocket engine, Figure 2, burns a stoichiometric mixture of fuel (liquid hydrogen) in oxidant (liquid oxygen).
The combustion chamber is cylindrical, 75 cm long and 60 cm in diameter, and the combustion process
produces 108 kg/s of exhaust gases. If combustion is complete, find the rate of reaction of hydrogen and of
oxygen.

Figure 2 Diagram for Example 1-1

Solution

The combustion of hydrogen in oxygen has the equation:

1
H ❑2 + O2 → H 2 O
2

We want to solve:

1 d H2 1 d O2
−r H = and −r O =
2
V dt 2
V dt

Solving for V which is the volume of the reactor:

( ) ( 100 m)=0.2121m
2
π 2 π 60 75 3
V = ( D ) h= m
4 4 100

The amount number of moles of H2O produced:

H 2 O produced=108 (
kg 1kmol
s 18 kg )
=6 kmol /s

So, from the chemical equation above:

kmol
H 2 used=6
s

kmol
O 2 used =3
s

Rate of reaction is:

−1 kmol 4 mol used

−r H = ∙6 =2.829 × 10
2
0.2121 m
3
s ( m3 rocket ) ∙ s
−1 kmol 4 mol used
−r O = ∙2 =1.415 ×10
2
0.2121m
3
s ( m3 rocket ) ∙ s

Example 1-2

A human being (75 kg) consumes about 6000 kJ of food per day. Assume that the food is all glucose and that
the overall reaction is
 Find man's metabolic rate (the rate of living, loving, and laughing) in terms of moles of oxygen used per m3 of
person per second.

Solution

The required is:

−1 d N O mol O2 used
r 'O' ' = = 3
2

2
V person dt ( m of person ) ∙ s
We can estimate that the density of the man is
3
ρ=1000 kg/m

Therefore, the volume of the person is:

75 kg 3
V person = 3
=0.075 m
1000 kg /m

Next, getting the needed O2

dNO
dt
2
=
( 2816
6000 kJ
kJ () 1 mol6 molglucose
2O
)=12.8 moldayO 2

mol glucose

Solving for the metabolic rate of the person:

''' 1 12.8 mol O2 used 1 day mol O2 used

−r O = 3
∙ =0.002 3
2
0.075 m day 24 × 3600 s m ∙s

IV. Self-Check
Quiz will be uploaded to the google classroom.

V. References
Laidler, K. (Britannica). (n.d.). chemical-kinetics. Retrieved January 19, 2022, from
https://www.britannica.com/science/chemical-kinetics
Levenspiel, O. (1999). Chemical reaction engineering (Third Edit). John Wiley & Sons, Inc.