Lecture on

Introduction & Overview to Heterogeneous Reactions

Instructor

Prof. Bishnupada Mandal

Room No. 102, Block - K
Department of Chemical Engineering
Indian Institute of Technology Guwahati

Copyright ©: All contents in this lecture, no matter the form it takes (whether digital, print, or
media) is protected under copyright law. The contents are only for the purpose of academic use.
Lecture 2: Introduction & Overview to Heterogeneous Reactions

Lecture Outline
• Brief Overview on Previous Lecture
• Classification of Reactions
• Definitions of Catalyst
• Catalyst Properties
• Catalytic Gas-Solid Interactions
• Turnover frequency
• Classification of Catalysts
 Classification of Reactions
There are many ways of classifying chemical reactions.
 In chemical reaction engineering probably the most useful
scheme is the breakdown according to the number and types of
phases involved.
 The big division being between the homogeneous and
heterogeneous systems.

 Homogeneous reaction: A reaction is homogeneous if it takes

place in one phase alone.
 Heterogeneous Reactions
How to define heterogeneous reaction in meaningful way?
 Any class of chemical reactions in which the reactants are components
of two or more phases (solid and gas, solid and liquid, two immiscible
liquids) or in which one or more reactants undergo chemical change at
an interface, e.g., on the surface of a solid catalyst.
 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.
 Complicating Factors

Two complicating factors that must be accounted for

beyond what is normally considered in homogeneous
systems.
 First: we have the complication of the rate expression,
and
 Second: the complication of the contacting patterns for
two-phase systems. Let us briefly discuss these in
turn.
 Complications of the Rate Equation
 Since more than one phase is present, the movement of
material from phase to phase must be considered in the rate
equation.
 Thus the rate expression in general will incorporate mass
transfer terms in addition to the usual chemical kinetics
term.
 These mass transfer terms are different in type and numbers
in the different kinds of heterogeneous systems.
 Hence, no single rate expression has general application.
See some simple examples given in Levenspiel (page 369 to
373).
 Contacting Patterns for Two-Phase Systems

 There are many ways that two phases can be contacted, and for
each the design equation will be unique.
 Design equations for ideal flow patterns may be developed
without too much difficulty.
 However, when real flow deviates considerably from these, we
can do one of two things:
o We may develop models to mirror actual flow closely, or
o We may calculate performance with ideal patterns which "bracket"
actual flow.
 Contacting Patterns for Two-Phase Systems
 Fortunately, most real reactors for heterogeneous systems can be
satisfactorily approximated by one of the five ideal flow patterns of
Fig. 1.
 Classification of Reactions
 Cutting across this classification is the catalytic reaction whose
rate is altered by materials that are neither reactants nor products.
 These foreign materials, called catalysts, need not be present in
large amounts.
 Catalyst
 Catalysts have been used by humankind for over 2000 years.

 The first observed uses of catalysts were in the making of

wine, cheese, and bread.

 It was found that it was always necessary to add small

amounts of the previous batch to make the current batch.

 However, it wasn't until 1835 that Berzelius began by

suggesting that small amounts of a foreign substance could
greatly affect the course of chemical reactions. This mysterious
force attributed to the substance was called catalytic.
 Catalyst
 In 1894, Ostwald expanded Berzelius' explanation by stating
that catalysts were substances that accelerate the rate of
chemical reactions without being consumed.

 During the 185 years since Berzelius' work, catalysts have come
to play a major economic role in the world market.

 It was found that it was always necessary to add small

amounts of the previous batch to make the current batch.

 It is estimated that well over 50% of all the chemical products

produced today are made with the use of catalysts.
 Catalyst
 Consider petroleum: Since this consists of a mixture of many
compounds, primarily hydrocarbons, its treatment under extreme
conditions will cause a variety of changes to occur
simultaneously, producing a spectrum of compounds, some
desirable, others undesirable.

 When a variety of reactions are encountered, the most important

characteristic of a catalyst is its selectivity.

 Catalyst only changes the rates of certain reactions, often a single

reaction, leaving the rest unaffected.

 Thus, in the presence of an appropriate catalyst, products

containing predominantly the materials desired can be obtained
from a given feed.
 Definitions of Catalyst
 A catalyst is a substance that affects the rate of a reaction
but emerges from the process unchanged.
 A catalyst usually changes a reaction rate by promoting a
different molecular path ("mechanism") for the reaction.
 For example, gaseous hydrogen and oxygen are virtually inert at
room temperature, but react rapidly when exposed to platinum.
 Definitions of Catalyst
 The development and use of catalysts is a major part of the
constant search for new ways of increasing product yield and
selectivity from chemical reactions.
 Because a catalyst makes it possible to obtain an end product by a
different pathway with a lower energy barrier, it can affect both the
yield and the selectivity.
 Normally when we talk about a catalyst, we mean one that
speed up a reaction, although strictly speaking, a catalyst can
either accelerate or slow the formation of a particular product
species.
 A catalyst changes only the rate of a reaction; it does not affect the
equilibrium.
 Definitions of Catalyst
 In heterogeneous catalytic reaction usually the catalyst is a
solid and the reactants and products are in liquid or gaseous
form.
 One example is the production of benzene, which is mostly
manufactured today from the dehydrogenation of cyclohexane
(obtained from the distillation of crude petroleum) using platinum-
on-alumina as the catalyst:
Importance of Catalyst and Types of Heterogeneous Reactions
 The simple and complete separation of the fluid product mixture
from the solid catalyst makes heterogeneous catalysis
economically attractive, especially because many catalysts are
quite valuable and their reuse is demanded.
 A heterogeneous catalytic reaction occurs at or very near the
fluid-solid interface.
 The principles that govern heterogeneous catalytic reactions
can be applied to both catalytic and noncatalytic fluid-solid
reactions.
 The two other types of heterogeneous reactions involve gas-liquid
and gas-liquid-solid systems.
 Reactions between gases and liquids are usually mass-transfer
limited.
 Catalyst Properties
 Because a catalytic reaction occurs at the fluid-solid interface,
a large interfacial area is almost always essential in attaining
a significant reaction rate.
 In many catalysts, this area is provided by an inner porous
structure (i.e., the solid contains many fine pores, and the
surface of these pores supplies the area needed for the high
rate of reaction).
 The area possessed by some porous catalysis materials is
surprisingly large.
 A typical silica-alumina cracking catalyst has a pore volume of
0.6 cm3/g and an average pore radius of 4 nm. The
corresponding surface area is 300 m2/g of these porous catalysts.
 Catalyst Properties
 Sometimes pores are so small that they will admit small molecules
but prevent large ones from entering.
 Materials with this type of pore are called molecular sieves.
 They may be derived from natural substances such as certain
clays and zeolites, or may be totally synthetic, such as some
crystalline aluminosilicates (see Figure a).
 Catalyst Properties
 These sieves can form the basis for quite selective catalysts.
 The pores can control the residence time of various molecules near
the catalytically active surface to a degree that essentially allows
only the desired molecules to react.
 One example of the high selectivity of zeolite catalysts is the formation
of para-xylene from toluene and methane shown in Figure b.
Catalyst Properties
 Here, benzene and toluene enter through the
zeolite pore and react on the interior surface
to form a mixture of ortho-, meta-, and para-
xylenes.
 However, the size of the pore mouth, is
such that only para-xylene can exit
through the pore mouth, as meta- and ortho-
xylene with their methyl group on the side
cannot fit through the pore mouth.
 There are interior sites that can isomerize
ortho- and meta- to para-xylene.
 Hence we have a very high selectivity to form
para-xylene.
 Catalyst Properties
 In some cases a catalyst consists of minute particles of an active
material dispersed over a less active substance called a support.
 The active material is frequently a pure metal or metal alloy.
 Such catalysts are called supported catalysts, as distinguished from
unsupported catalysts.
 Catalysts can also have small amounts of active ingredients added
called promoters, which increase their activity.
 Examples of supported catalysts are the packed-bed catalytic converter
in an automobile, the platinum-on-alumina catalyst used in
petroleum reforming, and the vanadium pentoxide on silica used to
oxidize sulfur dioxide in manufacturing sulfuric acid.
 On the other hand, platinum gauze for ammonia oxidation and
promoted iron for ammonia synthesis typify unsupported catalysts.
 Catalytic Gas-Solid Interactions
 For a catalytic reaction to occur, at least one and frequently all of
the reactants must become attached to the surface.
 This attachment is known as adsorption and takes place by two
different processes: physical adsorption and chemisorption.
 Physical adsorption is similar to condensation. The process is
exothermic, and the heat of adsorption is relatively small, being on
the order of 1 to 15 kcal/mol.
 The forces of attraction between the gas molecules and the solid
surface are weak. These van der Waals forces consist of interaction
between permanent dipoles, between a permanent dipole and an
induced dipole, and/or between neutral atoms and molecules.
 The amount of gas physically adsorbed decreases rapidly with
increasing temperature, and above its critical temperature only very
small amounts of a substance are physically adsorbed.
 Catalytic Gas-Solid Interactions
 The type of adsorption that affects the rate of a chemical
reaction is chemisorption.

 Here, the adsorbed atoms or molecules are held to the

surface by valence forces of the same type as those that
occur between bonded atoms in molecules.

 As a result, the electronic structure of the chemisorbed

molecule is perturbed significantly, causing it to be extremely
reactive.

 Interaction with the catalyst causes bonds of the adsorbed

reactant to be stretched, making them easier to break.
 Catalytic Gas-Solid Interactions
 Bonding from adsorption of
ethylene on a platinum
surface to form
chemisorbed ethylidyne.
 Chemisorption is an
exothermic process, but the
heats of adsorption are
generally of the same
magnitude as the heat of a
chemical reaction (i.e. 40 to
400 kJ /mol).
 Catalytic Gas-Solid Interactions
 In a landmark contribution to catalytic theory, Taylor suggested that a
reaction is not catalyzed over the entire solid surface but only at certain
active sites or centers.
 He visualized these sites as unsaturated atoms in the solids that resulted
from surface irregularities, dislocations, edges of crystals, and cracks along
grain boundaries.
 Other investigators have taken exception to this definition, pointing out that
other properties of the solid surface are also important.
 The active sites can also be thought of as places where highly reactive
intermediates (i.e., chemisorbed species) are stabilized long enough to react.
 This stabilization of a reactive intermediate is key in the design of any
catalyst.
 Consequently, for our purposes we will define an active site as a point on the
catalyst surface that can form strong chemical bonds with an adsorbed atom or
molecule.
 Turnover Frequency
 One parameter used to quantify the activity of a catalyst is the
turnover frequency (TOF), f.

 It is the number of molecules reacting per active site per

second at the conditions of the experiment.

 When a metal catalyst such as platinum is deposited on a

support, the metal atoms are considered active sites.

 The dispersion, D, of the catalyst is the fraction of the metal

atoms deposited that are on the surface.
 Classification of Catalysts
 One common way to classify catalysts is in terms of the type of
reaction they catalyze.
 List of representative reactions and their corresponding catalysts.

 Suppose we want to form styrene

from an equimolar mixture of
ethylene and benzene.
 We could carry out an alkylation
reaction to form ethylbenzene,
which is then dehydrogenated to
form styrene.
 We need both an alkylation catalyst
and a dehydrogenation catalyst.