Classification of Catalysis

What Is Catalyst in Chemistry?

In Chemistry, catalysts are defined as those substances which alter the rate of reaction by changing
the path of reaction. Most of the time, a catalyst is used to speed up or increase the rate of the
reaction. However, if we go to a deeper level, catalysts are used to break or rebuild the chemical
bonds between the atoms which are present in the molecules of different elements or compounds.
In essence, catalysts encourage molecules to react and make the whole reaction process easier and
more efficient.

Some of the important characteristic features of catalysts are given below:

A catalyst does not initiate a chemical reaction.

A catalyst is not consumed in the reaction.

Catalysts tend to react with reactants to form intermediates and, at the same time, facilitate the
production of the final reaction product. After the whole process, a catalyst can regenerate.

A catalyst can be either in solid, liquid or gaseous forms. Some of the solid catalysts include metals or
their oxides, including sulphides and halides. Semi-metallic elements such as boron, aluminium and
silicon are also used as catalysts. Further, liquid and gaseous elements, which are in pure form, are
used as catalysts. Sometimes, these elements are also used along with suitable solvents or carriers.

The reaction which involves a catalyst in their system is known as a catalytic reaction. In other words,
a catalytic action is a chemical reaction between the catalyst and a reactant. This results in the
formation of chemical intermediates that can further react quite readily with each other or with
another reactant to form a product. However, when the reaction between the chemical
intermediates and the reactants occurs or takes place, the catalyst is regenerated.

The reaction modes between the catalysts and the reactants usually tend to vary widely, and in the
case of solid catalysts, it is more complex. Reactions can be acidbase reactions, oxidation-reduction
reactions, coordination complexes formation, as well as the production of free radicals. For solid
catalysts, the reaction mechanism is greatly influenced by surface properties and electronic or crystal
structures. Some types of solid catalysts, such as polyfunctional catalysts, can have several reaction
modes with the reactants.

Types of Catalysts with Examples

There are several types of catalysts that can be used depending on the need or requirement of the
chemical reaction. They are explained below.

Positive Catalysts

Catalysts that increase the rate of a chemical reaction are positive catalysts. It increases the rate of
reaction by lowering the activation energy barriers such that a large number of reaction molecules
are converted into products, and thereby the percentage of yield of products increases.

Positive catalyst example: In the preparation of NH3 by Haber’s process, iron oxide acts as a positive
catalyst and increases the yield of ammonia in spite of less reaction of nitrogen.

Negative Catalysts

Catalysts that decrease the rate of reaction are negative catalysts. It decreases the rate of reaction by
increasing the activation energy barrier, which decreases the number of reactant molecules to
transform into products, and hence the rate of reaction decreases.

Negative catalyst example: The decomposition of hydrogen peroxide into water and oxygen is
retarded by using acetanilide, and this acts as a negative catalyst to decrease the rate of
decomposition of hydrogen peroxide.

Promoter or Accelerators

A substance that increases the catalyst activity is known as a promoter or accelerator.

Example: In Haber’s process, molybdenum or a mixture of potassium and aluminium oxides act as
promoters.

Catalyst Poisons andSubstances that decrease the catalyst activity are known as catalyst poisons or
inhibitors.

Catalysis, in chemistry, the modification of the rate of a chemical reaction,

usually an acceleration, by addition of a substance not consumed during
the reaction. The rates of chemical reactions—that is, the velocities at
which they occur—depend upon a number of factors, including the
chemical nature of the reacting species and the external conditions to
which they are exposed. A particular phenomenon associated with the
rates of chemical reactions that is of great theoretical and practical
interest is catalysis, the acceleration of chemical reactions by substances
not consumed in the reactions themselves—substances known as
catalysts. The study of catalysis is of interest theoretically because of
what it reveals about the fundamental nature of chemical reactions; in
practice, the study of catalysis is important because many industrial
processes depend upon catalysts for their success. Fundamentally, the
peculiar phenomenon of life would hardly be possible without the
biological catalysts termed enzymes.

Nanoparticles: hydrogen peroxide

Nanoparticles: hydrogen peroxide

Key People: Jöns Jacob Berzelius Wilhelm Ostwald Sidney Altman Thomas
Robert Cech Richard F. Heck

Related Topics: acid-base catalysis catalyst poison promoter homogeneous

catalysis asymmetric organocatalysis

In a catalyzed reaction, the catalyst generally enters into chemical

combination with the reactants but is ultimately regenerated, so the
amount of catalyst remains unchanged. Since the catalyst is not
consumed, each catalyst molecule may induce the transformation of
many molecules of reactants. For an active catalyst, the number of
molecules transformed per minute by one molecule of catalyst may be as
large as several million.

Where a given substance or a combination of substances undergoes two

or more simultaneous reactions that yield different products, the
distribution of products may be influenced by the use of a catalyst that
selectively accelerates one reaction relative to the other(s). By choosing
the appropriate catalyst, a particular reaction can be made to occur to the
extent of practically excluding another. Many important applications of
catalysis are based on selectivity of this kind.

Since a reverse chemical reaction may proceed by reversal of the steps

constituting the mechanism of the forward reaction, the catalyst for a
given reaction accelerates the reaction in both directions equally.
Therefore, a catalyst does not affect the position of equilibrium of a
chemical reaction; it affects only the rate at which equilibrium is attained.
Apparent exceptions to this generalization are those reactions in which
one of the products is also a catalyst for the reaction. Such reactions are
termed autocatalytic.

Cases are also known in which the addition of a foreign substance, called
an inhibitor, decreases the rate of a chemical reaction. This phenomenon,
properly termed inhibition or retardation, is sometimes called negative
catalysis. Concentrations of the inhibitor may in some cases be much
lower than those of the reactants. Inhibition may result from

(1) a decrease in the concentration of one of the reactants because of

complex formation between the reactant and the inhibitor,
(2) a decrease in the concentration of an active catalyst (“poisoning” of
the catalyst) because of complex formation between the catalyst and the
inhibitor, or

(3) a termination of a chain reaction because of destruction of the chain

carriers by the inhibitor.

Homogeneous catalysis
When the catalyst and the reacting substances are present together in a
single state of matter, usually as a gas or a liquid, it is customary to
classify the reactions as cases of homogeneous catalysis. Oxides of
nitrogen serve as catalysts for the oxidation of sulfur dioxide in the lead
chamber process for producing sulfuric acid, an instance of homogeneous
catalysis in which the catalyst and reactants are gases. Traces of water
vapour catalyze some gas reactions—for example, the interaction of
carbon monoxide and oxygen, which proceeds only slowly in dry
conditions. Sulfuric acid used as a catalyst for the formation of diethyl
ether from ethyl alcohol is an example of homogeneous catalysis in the
liquid phase (when the products, water and ether, are continuously
removed by distillation); by this method, considerable quantities of alcohol
can be converted to ether with a single charge of sulfuric acid. The
inversion of cane sugar and the hydrolysis of esters by acid solutions also
are examples of homogeneous catalysis in the liquid phase.

The oxidation of sodium sulfite solutions by dissolved oxygen is greatly

accelerated by minute traces of copper ions in the homogeneous liquid
system. This system is of special interest since it has been shown that the
process is a chain reaction. In this case many thousands of molecules of
sodium sulfite can be oxidized to sulfate if the initial activation process is
produced by absorption of a limited number of quanta (discrete energy
measures) of light. The best example of a light-initiated chain reaction is
the photocombination of hydrogen (H2) and chlorine (Cl2); as many as
one million molecules of hydrogen chloride can be formed by absorption
of a single light quantum (designated hν).

Heterogeneous catalysis
Many catalytic processes are known in which the catalyst and the
reactants are not present in the same phase—that is, state of matter.
These are known as heterogeneous catalytic reactions. They include
reactions between gases or liquids or both at the surface of a solid
catalyst. Since the surface is the place at which the reaction occurs, it
generally is prepared in ways that produce large surface areas per unit of
catalyst; finely divided metals, metal gauzes, metals incorporated into
supporting matrices, and metallic films have all been used in modern
heterogeneous catalysis. The metals themselves are used, or they are
converted to oxides, sulfides, or halides.

With solid catalysts, at least one of the reactants is chemisorbed (a

portmanteau term for chemically adsorbed) by the catalyst. A catalyst is
chosen that releases the products formed as readily as possible; otherwise
the products remain on the catalyst surface and act as poisons to the
process. Chemisorption can occur over a wide temperature range, the
most effective temperature for adsorption depending on the nature of the
catalyst. Thus, hydrogen is chemisorbed readily by many metals even at
liquid air temperatures (below −180 °C [−290 °F]). With a series of
hydrogenationdehydrogenation catalysts—e.g., zinc oxide–chromic oxide
(ZnO–Cr2O3)— chemisorption of hydrogen often occurs above room
temperature. Nitrogen is rapidly chemisorbed on synthetic ammonia-iron
catalyst in the region above 400 °C (750 °F). It has been shown that iron
films chemisorb nitrogen even at liquid air temperatures, with additional
chemisorption found above room temperatures. It follows from such
considerations that whereas physical adsorptions, which parallel the ease
of liquefaction of the adsorbed substance, occur spontaneously,
chemisorption, which involves the making and breaking of chemical
bonds, often requires activation energies (energy needed to initiate
reactions) as do uncatalyzed chemical processes. To be efficient
catalytically, a process must involve energies of activation for all the steps
involved that, at their maxima, are less than those required for the
uncatalyzed reaction.

This situation is illustrated graphically in the figure, with a

hypothetical reaction that could occur by either an uncatalyzed or a
catalyzed route. Catalysis in stereoregular polymerization
The importance of the concept of adsorption of reactants on the surface of
catalysts has been greatly increased by the development of stereoregular
polymerization processes—that is, methods that yield polymers whose
molecules have definite threedimensional patterns. Such processes were
developed independently by the German chemist Karl Ziegler and the
Italian Giulio Natta. An example is the polymerization of propylene with a
titanium trichloride–alkyl aluminum catalyst. In the case of a generalized
ethylenic compound, CH2=CHR, stereoregular polymerization may yield
three different arrangements of the polymer: an isotactic polymer, a
syndiotactic polymer, and an atactic polymer. These have the following
arrangements of their molecular chains:

In the isotactic polymer the monomer units have added head-to-tail, to

give a series of C–R tertiary bonds with the same configuration in space;
in the syndiotactic polymer the tertiary carbon atoms in the chain have
alternate (dextro and levo) spatial configurations; and in the atactic
polymer there is no regularity in the distribution of steric configurations of
the asymmetric carbon atoms. The various polymeric forms differ in their
physical properties. Isotactic polypropylene, for example, has a density of
0.92 gram per cubic cm (0.53 ounce per cubic inch) and a melting point of
165 °C (329 °F), whereas an atactic polymer has a somewhat smaller
density, 0.85 gram per cubic cm (0.49 ounce per cubic inch), and a much
lower melting point of −35 °C (−30 °F). The more regular isotactic
polymer is denser and has a higher melting point than the atactic product
because of its greater tendency to crystallize (in spite of the fact that the
substituent R may be quite large, hindering crystal formation).
Stereoregular polymerization suggests a stereoregulated adsorption at the
active centres of the catalyst. In the case of polypropylene, the catalytic
centres have been identified by electron micrographs as α-TiCl3 surfaces,
which cover only a small fraction of the total surface area, whereas the β-
TiCl3 surfaces, which are more abundant, appear to be covered with
polymer. The difference between the α- and β-surfaces lies in the random
(α) and linear (β) arrangements of Ti3+ sites in the two surfaces.
Units
The derived SI unit for measuring the catalytic activity of a catalyst is
“katal”. It is further quantified in moles per second. If we want to describe
the productivity of a catalyst, it can be defined by the turnover number
(TON). Catalytic activity can be described by the turnover frequency
(TOF), which is TON per time unit. Besides, the enzyme unit is its
biochemical equivalent.

Photocatalysts
Photocatalysis is the phenomenon wherein the catalyst is able to receive
light (such as visible light) and be promoted to an excited state.

Autocatalysis
In the autocatalytic reaction, no specific catalyst is added. Instead, one of
the products acts as a catalyst and increases the rate of formation of
products.

Example 1: Decomposition of Arsene (AsH3) is formed by the Arsenic

formed in the reactor is “autocatalyst”.

2As H3 → 2As + 3H2

In this process, As acts as a catalyst.

Example 2: Oxidation of oxalic acid by KmnO4

When Permanganate is added to an acidic solution, oxidation of oxalate

ions (or oxalic acid) occurs. The reaction results in the formation of Mn2+
ions, and it auto-catalyses the reaction. The rate of reaction between
potassium permanganate and acidified oxalate solution is initially slow.
Mn+2+ ions that are formed during the reaction help in increasing the
rate of reaction.