KINETICS AND REACTOR DESIGN

Instructor: Dr. Debirupa

PART 1: OVERVIEW OF REACTIONS AND REACTORS

Kinetics & Reactor design (KRD), as the name suggests, is the study of chemical kinetics and
reactor design. In many Universities, this course is also called as “Chemical Reaction
Engineering” (CRE). CRE is the heart and soul of any chemical process, and thus an integral
part of almost all products that you see around you. Aside from chemical processes, principles
of CRE can be used in many “modern” applications such as wastewater treatment, degradation
of pollutants in the environment, biochemical engineering, pharmacokinetics, microelectronics
fabrication, disease modelling, nanomaterial synthesis, and so on.

The typical objective of KRD is to be able to design reactors or assess the performance of
existing reactors. To do this, we need to have knowledge and understanding of the 2 main
building blocks of KRD: (1) Reactions, and (2) Reactors.

How can we define a chemical reaction?

A process involving the chemical transformation of one or more substances into another. The
substances that undergo the transformation are called reactants, and the newly formed ones are
called products.
Reactants  Products
A+B  C+D

When it comes to reactions, there are 2 very important aspects that we need to understand: (1)
How fast does the reaction occur? (2) How much product can be formed under a given
set of conditions? The answers to these 2 questions are not only important in the context of
reactor design, but also often determines the economic feasibility of the process. A very slow
reaction and/or very little conversion of reactant to product is unlikely to be taken up by any
company for large-scale production, unless the demand of the product is very high or the
product is of high economic value.
Nomenclature

1. NA: Moles of reactant A [unit: mol]

*What is a mole? SI unit used to measure the amount of any substance. This unit is commonly
used in KRD. 1 mole = 6.022×1023 particles (atoms, molecules, ions, etc.)

2. t: time [unit: s, min, h]

3. FA: Molar flow rate of reactant A [unit: mol/time]

4. V: Volume of fluid [unit: L, m3, dm3]

5. v0: Volumetric flow rate [unit: volume/time]

6. CA: Molar concentration of reactant A [unit: mol/volume]

7. pA: Partial pressure of reactant A [unit: atm, bar]

8. yA: Mole fraction of reactant A

Types of reactions

1. Combination vs. Decomposition vs. Isomerization reactions

There are three main ways by which a substance can lose its chemical identity: by
combining with another substance (combination), by breaking down into two or more
smaller substances (decomposition), or by rearrangement / change in configuration
(isomerization)

 PCl5  PCl3 + Cl2

 92U
238
 90Th234 + 2He4
  N2 + O2  2NO
 2H2 + O2  2H2O
 C2H5CH=CH2  CH2=C(CH3)2
 cis-2-butene  trans-2-butene

2. Reversible vs. Irreversible reactions

Irreversible reaction is one that proceeds in only one direction, whereas a reversible
reaction can proceed in either direction depending on the concentration of product/reactant
relative to the equilibrium concentration. Strictly speaking, no chemical reaction is
completely irreversible, it is just that their equilibrium point lies very close to the product
side.

 Ethane  Ethylene + Hydrogen

 Cumene ↔ Benzene + Propylene
 Nitrogen + Hydrogen ↔ Ammonia

3. Single vs. Multiple reactions

When a single stoichiometric equation represents a reaction, it is a single reaction. When

more than one equation is used to represent the observed changes, it is a multiple reaction.
Multiple reactions may be in series or in parallel.

Single reaction: A+B  C+D

Series reaction: A+B  C  D

Parallel reaction: A C, A  D

4. Homogenous vs. Heterogeneous reactions

A homogenous reaction is one which 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. Examples of heterogeneous reactions include burning of coal, roasting of ores, attack
of solids by acid, gas-liquid absorption with reaction, etc. Gas-phase or liquid-phase
reactions involving solid catalysts are also heterogeneous in nature.

5. Catalytic vs. Non-catalytic reactions

*What is a catalyst?

A catalyst is a “foreign” material that is neither a reactant nor a product but has the ability
to alter the rate of a reaction. Reactions that take place in the presence of a catalyst are
 catalytic reactions. If the catalyst is in the same phase as that of reactants and products, it
is a homogenous catalytic reaction. Usually, catalysts are solids and reactants/products are
either in a liquid or a gaseous phase. Hence, most catalytic reactions are heterogeneous in
nature. Examples include ammonia synthesis, ammonia oxidation to nitric acid, cracking
of crude oil, conversion of SO2 to SO3, etc.

6. Constant volume vs. Variable volume reactions

If the volume remains constant throughout the course of a reaction, it is a constant volume
reaction. Liquid-phase reactions are considered to be constant volume because of negligible
changes in density. Gas-phase reactions are usually variable volume in nature. However,
gas-phase reactions may also be considered constant volume if they are carried out in a
sealed vessel (with appropriate pressure monitoring) or if there are no changes in the
number of moles between reactants and products.

A(g) + B(g)  C(g) + D(g)

7. Exothermic vs. Endothermic reactions

Reactions with positive heat of reaction are endothermic (heat is absorbed from
surroundings), whereas those with negative heat of reaction are exothermic (heat is released
into surroundings).

Types of ideal reactors

A reactor is an equipment for carrying out any reaction. There are 2 main categories of reactors:
batch reactor and flow reactors. Within flow reactors, there are 2 types with different
“contacting pattern”: Continuous Stirred Tank Reactor (CSTR) and Plug Flow Reactor
(PFR). Batch, CSTR, and PFR constitute the 3 basic types of ideal reactors.

1. Batch reactor

A batch reactor is simply a vessel/tank that holds all the “contents” while they react to form
products. Typically, all the reactants are added to the reactor and the contents are mixed
using an agitator. The reaction is allowed to proceed for a given time, then the reactor is
turned off and the contents are emptied. The reactor is cleaned and is made ready for the
next batch. The main characteristic of a batch process is that the composition of the system
continuously changes with time as the reaction proceeds. Hence, a batch reactor is an
unsteady-state reactor.
 Advantages: It is a relatively simple reactor by design, which is useful for small-scale and
lab-scale reactions. It is extensively used for studying reaction kinetics. High conversions
can be achieved if the reactants are allowed to react for a sufficiently long period of time.

Disadvantages: High labor cost/batch; variations across batches; difficulty in large-scale

manufacture.

2. Flow reactors

As the name suggests, in any ideal flow reactor, there is a continuous flow of reactants into
the reactor and a continuous flow of products out of the reactor.

(a) CSTR or Mixed Flow Reactor (MFR) or backmix reactor

A CSTR is a flow reactor in which all the contents are “perfectly mixed”. Typically, in the
beginning, the reactant flow is started and the agitator is turned on. The product is not yet
withdrawn at this stage. This phase is called the start-up phase. During this time, the
composition within the reactor changes with time. After some time, the product outlet is
opened and thereafter, the composition of the reactor does NOT change with time or spatial
location and the CSTR becomes a steady-state reactor.
Advantages: No batch to batch variations; product is of uniform quality; low labor cost;
suitable for large-scale production; easier to control temperature

Disadvantages: Lower conversion per unit volume

(b) PFR or Tubular Flow Reactor

Unlike a CSTR which is shaped like a vessel/tank, the PFR is shaped like a cylindrical tube
or a pipe. The reactants enter on one end of the tune and the product exits from the other
end of the tube. The reactants react as they flow along the length of the tube, and hence
composition changes with spatial location (along the length or volume of the reactor). At a
particular location, composition does NOT change with time, and hence the PFR is also a
steady-state reactor. In an ideal PFR, the flow of the fluid is assumed to be like a “plug”
with no radial variation in velocity, temperature, or concentration.

Advantages: PFR is suitable for gas-phase reactions; low labor cost; higher conversion
per unit volume; high heat transfer area.

Disadvantages: Undesired temperature gradients may exist; poor temperature control;

difficult to clean.
(c) Packed bed reactor (PBR)

A PBR is similar to a PFR, just that it is filled with a solid packing (usually a catalyst).
Thus, it is mostly used for solid-catalyzed gaseous reactions. A PBR has the same
characteristics of PFR: steady-state and composition changes with length of the reactor.