Lecture 2

Introduction & Overview to Heterogeneous Reactions

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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 reaction: 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.

For these systems there are 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.

The 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 these 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: we may develop models to mirror actual
flow closely, or we may calculate performance with ideal patterns which "bracket" actual flow.
Fortunately, most real reactors for heterogeneous systems can be satisfactorily approximated by
one of the five ideal flow patterns of Fig. 1. Notable exceptions are the reactions which take place
in fluidized beds. There special models must be developed.
 Fig. 1. Ideal contacting patterns for two flowing fluids.

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. Catalysts act somehow as go-betweens, either hindering or accelerating the reaction
process while being modified relatively slowly if at all.

Table 1 shows the classification of chemical reactions according to our scheme with a few
examples of typical reactions for each type.

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 to tie together observations of earlier chemists 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.

In 1894, Ostwald expanded Berzelius' explanation by stating that catalysts were substances
that accelerate the rate of chemical reactions without being consumed. During the 175 years
since Berzelius' work, catalysts have come to play a major economic role in the world market.
It is estimated that well over 50% of all the chemical products produced today are made with the
use of catalysts.

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.
Although a catalyst can easily speed the rate of reactions a thousandfold or a millionfold, still,
when a variety of reactions are encountered, the most important characteristic of a catalyst is its
selectivity. By this we mean that it 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. The reaction coordinate
shown in Figure 2 is a measure of the progress along the reaction path as H2 and O2 approach
each other and pass over the activation energy barrier to form H 2O.

Fig. 2. Different reaction paths

Catalysis is the occurrence, study, and use of catalysts and catalytic processes. Commercial
chemical catalysts are immensely important. Approximately one third of the material gross
national product of the United States involves a catalytic process somewhere between raw
material and finished product.

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.

The 2007 Nobel Prize for chemistry was awarded to Gerhard Ertl for his pioneering work on
heterogeneous catalytic reactions. 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:

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. Examples include the Raney nickel used in
the hydrogenation of vegetable and animal oils, platinum-on-alumina used in the reforming
of petroleum naphthas to obtain higher octane ratings, and promoted iron used in ammonia
synthesis.

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, and 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 3a). 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 3b.
 Fig. 3. (a) Framework structures and (b) pore cross sections of two types of zeolites.

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.

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, promoted iron for ammonia synthesis,
and silica-alumina dehydrogenation catalyst used in butadiene manufacture typify unsupported
catalysts.

Catalytic Gas-Solid Interactions

For the moment, let us focus our attention on gas-phase reactions catalyzed by solid surfaces. 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.
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.

Figure 4 shows the bonding from the adsorption of ethylene on a platinum surface to form
chemisorbed ethylidyne. Like physical adsorption, 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). If a catalytic reaction involves chemisorption, it must be
carried out within the temperature range where chemisorption of the reactants is appreciable.

Fig. 4. Ethylidyne chemisorbed on platinum

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. Table
2 gives a list of representative reactions and their corresponding catalysts.

Table 2. Types of reaction and representative catalysts

If, for example, we were 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: